Garment incorporating aqueous polyurethane dispersions having altered stress profile

ABSTRACT

Articles, such as garments, including films comprising dried aqueous polyurethane dispersions are disclosed, whereby the garment has an altered stress which is exhibited during wear of the garment. The film may be bonded to the fabric of the article to provide a fabric or film laminate.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No.62/376,003 filed on Aug. 17, 2016, and is a continuation-in-part of U.S.application Ser. No. 15/161,749, filed on May 23, 2016, which claims thebenefit of U.S. Provisional Application No. 61/021,241 filed on Jan. 15,2008. The entire contents of the aforementioned applications areincorporated by reference herein.

BACKGROUND OF THE INVENTION Field of the Invention

The present invention relates to garments including body shapinggarments and performance enhancing garments that include an alteredstress profile. The garment includes one or more layers of material suchas fabric and/or polyurethane foam in combination with an aqueousdispersion.

Summary of Related Technology

Garments provide a variety of different functions including, but notlimited to, warmth, fashion, and comfort. Two goals of body shapinggarments include support and comfort either of which can be compromiseddue to the other. One reason for reduction in comfort is that garmentsdesigned for body-shaping or support frequently have areas whereincreased pressure is exerted on the wearer of the garment.

The areas of increased pressure can result in discomfort to the wearer.Therefore, there is a need for garments that overcome these deficienciesby redistributing the pressure by altering the stress profile of thegarment, including providing additional support where desired, andproviding greater comfort to the wearer.

Another issue experienced by body-shaping garments, such as laminatedfoam garments, is fabric growth. This is particularly an issue withone-piece laminated foam brassieres. There is a need to provide a methodof redistributing or controlling stress within the garment to preventfabric growth.

SUMMARY OF THE INVENTION

A garment is disclosed herein including: one or more sections of fabric,wherein each section of fabric has a stress profile; and one or morefilms adhered to one or more sections of fabric to form a fabriclaminate having an altered stress profile. Each film comprises a driedaqueous polyurethane dispersion comprising a prepolymer and theprepolymer comprises: a glycol, an aliphatic diisocyanate and a diol. Aratio of isocyanate groups in the aliphatic diisocyanate to hydroxygroups in the glycol and the diol (NCO/OH) is about 1.30 to about 2.20.The aliphatic diisocyanate may be 4,4′-methylene bis (cyclohexylisocyanate); the glycol may be a poly(tetramethylene ether) glycol; andthe diol may be DMPA. In an embodiment, a concentration range ofcarboxylic acid groups in milliequivalent per kg of prepolymer (MeqAcid/kg CG) is about 140 to about 250.

In certain embodiments, the garment may be a brassiere, bralette,swimwear, active wear or a shaper. For example, the film may extendacross a bust, belly, thigh, seat, or any combination thereof of thegarment, or across the wing portion of the brassiere or bralette.

The fabric laminate having an altered stress profile also may exhibitimproved tensile strength, whiteness retention and/or chlorineresistance.

Methods of preparing garments including an altered stress profile arealso included.

Another embodiment is a bust supporting garment comprising: a materialdefining a breast cup including a lower periphery and a side peripherythat extends from said lower periphery to a top portion of the breastcup where a strap is optionally attached, and a winged portion; and afilm adhered to at least a portion of the material. The film comprises adried aqueous polyurethane dispersion including a prepolymer, and theprepolymer comprises: a glycol, an aliphatic diisocyanate and a diol. Aratio of isocyanate groups in the aliphatic diisocyanate to hydroxygroups in the glycol and the diol (NCO/OH) is about 1.30 to about 2.20.The film may be adhered to the material at the lower and/or sideperipheries of the breast cups, the wing portions, and/or the straps ofthe garment. The bust supporting garment may be a brassiere, bralette orsports bra.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a portion of fabric including a geometrically inverted filmof dried aqueous dispersion.

FIG. 2 shows a portion of fabric including a geometrically inverted filmof dried aqueous dispersion.

FIG. 3 shows a portion of fabric including a narrow strip of film ofdried aqueous dispersion.

FIG. 4 shows a brassiere including film regions along a lower and sideperiphery.

FIG. 5 shows a brassiere including film regions.

FIG. 6 shows a brassiere including film regions.

FIG. 7 shows a brassiere including film regions.

FIG. 8 shows a portion of fabric including a triangular shaped filmregion.

FIG. 9 shows a portion of fabric including a triangular shaped filmregion.

FIG. 10 shows a panty including film regions.

FIG. 11 shows a panty including film regions.

FIG. 12 shows a film on a substrate.

FIG. 13 shows a film between two substrates.

FIG. 14 shows a portion of fabric including a film region.

FIG. 14A shows a multiple layer portion of fabric including a filmregion.

FIG. 15 shows a portion of fabric including a film region.

FIG. 15A shows a multiple layer portion of fabric including a filmregion.

FIG. 16 shows a cross-section of the multiple layer fabric of FIG. 14Aalong line X-X.

FIG. 17 is a graphic representation of the set % of garments laminatedwith polymer compositions.

FIG. 18 is a graphic representation of a control fabric compared to afilm.

FIG. 19 is a graphic representation of a stress/strain analysis.

FIG. 20 is a graphic representation of a stress/strain analysis

FIG. 21 is a bar graph depicting film whiteness retention for six filmsamples after thermal exposure.

FIG. 22 is a bar graph depicting film whiteness retention for six filmsamples after UV exposure.

FIG. 23 is a bar graph depicting film whiteness retention for six filmsamples after NO₂ exposure.

DETAILED DESCRIPTION OF THE INVENTION

A garment is disclosed herein wherein a film is adhered to one or moresections of fabric to form a fabric laminate having an altered stressprofile.

The term “film” is used herein to describe a layer (or layers) having alength and width of dried aqueous polyurethane dispersion, that may ormay not require application to a substrate for support. The film may becontinuous or discontinuous, shaped or free-formed. In an embodiment,the film may be substantially two-dimensional and/or relatively flat.

The term “fabric laminate” refers to an article or garment including atleast one fabric layer and at least one film layer that have beenattached or bonded together. The methods of attachment include, but arenot limited to, gluing, heating, application of pressure, padding,coating, printing, bonding, laminating or other treatment methods, andthen may be cured (or dried) with a residence time of about 1 to about 5minutes. Upon drying, such an article or garment exhibits higher stretchand recovery, improved chlorine resistance, and improved whitenessretention, among other benefits.

The term “stress profile” as used herein refers to a physical pressure,pull, or other force that is exerted on a fabric accounting for variousdifferent forces that can be measured at various points throughout thegarment. The stress profile can be observed in any fabric such as afabric used in a garment. One example of a stress profile of a fabric isnoted for body shaping garments where the stress or pressure exerted onthe garment will vary as the garment is being worn due to wearermovement. Another example is for a support garment such as a brassierewhere the stress on the bottom of the breast cup portions may be greaterthan that on the top of the breast cup portions. The stress profile maybe quantitatively measured, for example, by calculating tensile strengthand associated properties.

As used herein, the term “modulus”, also known as the elastic modulus,is a measure of the stiffness of a fabric.

The term “geometrically inverted” is meant to include embodiments wherea film of the same geometric shape as the fabric with which it will belaminated has been rotated with respect to the fabric. The film may belarger, smaller, or the same size as the fabric section. This alsoincludes, but is not limited to, where film and fabric of size anddimension are designed inversely proportionate to the modulus of thefilm and fabric, respectively.

As used herein, the term “non-linear” includes shapes other than astraight line. This includes, but is not limited to, curved shapes, arcshapes, and wavy shapes.

As used herein, the term “narrow strip” refers to a shape having alength and a width where the length is at least twice the width. Thelength may vary and depends on the size of the garment to which it isapplied.

As used herein, the term “porous” refers to a substrate that includesvoids or holes in the surface or at any point within or through thethickness of the substrate or to any material of which the articles ofthe present invention may come into contact.

As used herein, the term “pressing” or “pressed” refers to an articlethat has been subjected to heat and/or pressure to provide asubstantially planar structure.

As used herein, the term “foam” refers to any suitable foam that may beused in fabric construction such as polyurethane foam.

As used herein, the term “dispersion” refers to a system in which thedisperse phase consists of finely divided particles. A continuous phasecan be a liquid, solid or gas.

As used herein, the term “aqueous polyurethane dispersion” refers to acomposition containing at least a polyurethane or polyurethane ureapolymer or prepolymer (such as the polyurethane prepolymer describedherein), optionally including a solvent, that has been dispersed in anaqueous medium, such as water, including de-ionized water.

A dried aqueous polyurethane dispersion, as used herein, is an aqueouspolyurethane dispersion that has been subjected to curing or drying byany suitable method. The dried aqueous polyurethane dispersion may be inthe form of a shaped article, e.g., a film.

As used herein, the term “solvent,” unless otherwise indicated, refersto a non-aqueous medium, wherein the non-aqueous medium includes organicsolvents, including volatile organic solvents (such as acetone) andsomewhat less volatile organic solvents (such as MEK, or NMP).

As used herein, the term “solvent-free” or “solvent-free system” refersto a composition or dispersion wherein the bulk of the composition ordispersed components has not been dissolved or dispersed in a solvent.

As used herein, the term “article” refers to a formed substrate ortextile fabric. The article may be a garment. The article may comprise adried aqueous polyurethane dispersion, which may be in the form of ashaped article, and a substrate, for example a textile fabric, which mayor may not have at least one elastic property, in part, due to theapplication of the aqueous polyurethane dispersion or shaped article asdescribed herein. The article may be in any suitable configuration suchas one-dimensional, two-dimensional and/or three-dimensional.

As used herein, the term “shaped article” may refer to one of a numberof objects including for example, film, tape, dots, webs, stripes, bead,and foam. In an embodiment, the shaped article is a film. A film maydescribe a sheet material of any shape. A tape may describe a film innarrow strip form. A film may be in the form of a tape. The shapedarticle is a layer comprising an aqueous polyurethane dispersioncontaining the polyurethane prepolymer described herein, which may bedried, and may be applied to a substrate or release paper, which can beused for adhesion and/or to form a rigid or an elastic article.

As used herein, the term “fabric” or “textile fabric” refers to aknitted, woven or nonwoven material. The knitted fabric may be flatknit, circular knit, warp knit, narrow elastic, and lace. The wovenfabric may be of any construction, for example sateen, twill, plainweave, oxford weave, basket weave, and narrow elastic. The nonwovenmaterial may be meltblown, spun bonded, wet-laid, carded fiber-basedstaple webs, and the like. Fabrics suitable for use herein include butare not limited to cotton, wool, acrylic, polyamide (nylon), polyester,spandex, regenerated cellulose, rubber (natural or synthetic), bamboo,silk, soy or combinations thereof.

As used herein, the term “substrate” refers to any material to which ashaped article or aqueous polyurethane dispersion can be applied. Asubstrate may be substantially one dimensional as in a fiber, twodimensional as in a planar sheet, or a three dimensional article or abumpy sheet. A planar sheet for example may comprise textile fabric,paper, flocked article, and/or web. A three dimensional article forexample may comprise leather and/or foam. Other substrates may comprisewood, paper, plastic, metal, and composites such as concrete, asphalt,gymnasium flooring, and plastic chips.

As used herein, the term “hard yarn” refers to a yarn which issubstantially non-elastic.

As used herein, the term “molded” article refers to a result by whichthe shape of an article or shaped article is changed in response toapplication of heat and/or pressure.

As used herein, the term “derived from” refers to forming a substanceout of another object. For example, a film may be derived from a aqueousdispersion which can be dried.

As used herein, the term “modulus” refers to a ratio of the stress on anitem expressed in force per unit linear density or area.

As used herein, the term “fabric growth” is meant to include the naturaltendency of fabrics to stretch over time or during wear that is notrecovered (i.e., not elastic).

As used herein, the term “performance-enhancing” in reference to agarment refers to a garment that reduces fatigue or maintainsperformance-ability of the wearer of the garment. For example, anathlete may wear a performance-enhancing garment during competition toreduce fatigue and/or maintain competitive performance.

In some embodiments, a garment includes a film that alters the stressprofile of the garment. This includes equally distributing stressthroughout the garment as well as providing a “stress gradient” whereadditional support is desired. The stress gradient provides areas ofpreselected stress to redistribute the stress such as from an area oflower stress to an area of greater stress within the fabric of thegarment. One example of a stress gradient is useful for a bustsupporting garment, such as a brassiere, sports bra or bralette (thatis, a brassiere without underwire). The film may be included in a breastcup to provide a stress gradient that provides greater stress forsupport at the bottom of the breast cup and lower stress at the top ofthe breast cup. The film may also be applied to a wing portion, strap,and/or bridge of the bust supporting garment. The breast cup isunderstood to be the portion of the material that, when worn, holds andsupports the breast. The breast cup need not contain underwire, seams,padding, lining, foam, panels, or the like defining the area. In certainembodiments, the breast cup may comprise a pair of breast cups thatinclude underwire, seams, padding, lining, foam, panels, or the like. Inother embodiments, the breast cup may be a piece of material used in,for example, a simple bralette or sports bra, formed without underwire,seams, padding, lining, foam, panels, or the like defining the area.

An article of the disclosure may include at least one layer of a filmsuch as comprising a dried aqueous polyurethane dispersion on one ormore sections of fabric. The articles may have more than one layer offabric and/or more than one layer of film. The film may provide stretchand recovery, increased elastic modulus, adhesion, moldability, shaperetention, and flexibility properties for the article. These articlesmay be formed into fabrics and/or garments.

The film of the disclosure may optionally be cast from a solution, anaqueous polyurethane dispersion, or a substantially solvent free aqueousdispersion. Specific examples of aqueous polyurethane dispersions andfilms cast from them which are useful with the present invention aredescribed hereinbelow. Aqueous polyurethane dispersions used herein aremade from prepolymers comprising a glycol, an aliphatic diisocyanate anda diol, such as those disclosed in PCT Application titled: AqueousPolyurethane Dispersions, Prepolymers, and Shaped Articles MadeTherefrom, filed on the same day herewith, which is incorporated byreference herein in its entirety.

Glycol components suitable as a starting material for preparingprepolymers disclosed herein include polycarbonates, and polyesters,polycarbonate glycols, polyether glycols, and polyester glycols.

Examples of polyether glycols that can be used include, but are notlimited to, those glycols with two or more hydroxy groups, fromring-opening polymerization and/or copolymerization of ethylene oxide,propylene oxide, trimethylene oxide, tetrahydrofuran, and3-methyltetrahydrofuran, or from condensation polymerization of apolyhydric alcohol, preferably a diol or diol mixtures, with less than12 carbon atoms in each molecule, such as ethylene glycol,1,3-propanediol, 1,4-butanediol, 1,5-pentanediol 1,6-hexanediol,neopentyl glycol, 3-methyl-1,5-pentanediol, 1,7-heptanediol,1,8-octanediol, 1,9-nonanediol, 1,10-decanediol and 1,12-dodecanediol. Alinear, bifunctional polyether polyol is preferred, and apoly(tetramethylene ether) glycol of molecular weight of about 1,700 toabout 2,100, such as Terathane® 1800 (Invista) with a functionality of2, is used in an embodiment.

Examples of polyester glycols that can be used include those esterglycols with two or more hydroxy groups, produced by condensationpolymerization of aliphatic polycarboxylic acids and polyols, or theirmixtures, of low molecular weights with no more than 12 carbon atoms ineach molecule. Examples of suitable polycarboxylic acids are malonicacid, succinic acid, glutaric acid, adipic acid, pimelic acid, subericacid, azelaic acid, sebacic acid, undecanedicarboxylic acid anddodecanedicarboxylic acid. Example of suitable polyols for preparing thepolyester polyols are ethylene glycol, 1,3-propanediol, 1,4-butanediol,1,5-pentanediol 1,6-hexanediol, neopentyl glycol,3-methyl-1,5-pentanediol, 1,7-heptanediol, 1,8-octanediol,1,9-nonanediol, 1,10-decanediol and 1,12-dodecanediol. A linear,bifunctional polyester polyol with a melting temperature of about 5° C.to about 50° C. is used in an embodiment.

Examples of polycarbonate glycols that can be used include thosecarbonate glycols with two or more hydroxy groups, produced bycondensation polymerization of phosgene, chloroformic acid ester,diallyl carbonate or diallyl carbonate and aliphatic polyols, or theirmixtures, of low molecular weights with no more than 12 carbon atoms ineach molecule. Example of suitable polyols for preparing thepolycarbonate polyols are diethylene glycol, 1,3-propanediol,1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol,3-methyl-1,5-pentanediol, 1,7-heptanediol, 1,8-octanediol,1,9-nonanediol, 1,10-decanediol and 1,12-dodecanediol. A linear,bifunctional polycarbonate polyol with a melting temperature of about 5°C. to about 50° C. is used in an embodiment.

In an embodiment, the prepolymer contains at least about 60%, at leastabout 65%, or at least about 70% of the glycol, based upon total weightof the prepolymer. In another embodiment, the prepolymer contains about60% to about 85%, about 65% to about 80%, about 68% to about 78%, orabout 70% to about 77% of the glycol, based upon total weight of theprepolymer.

Any aliphatic diisocyanate may be used in the disclosure. In anembodiment, the isocyanate is a dicyclohexylmethane diisocyanate,preferably including a mixture of its isomers. An example of a suitableisocyanate component is a dicyclohexylmethane diisocyanate or4,4′-methylene bis (cyclohexyl isocyanate) (“PICM”) such as Vestanate®H12MD1 (Evonik) or Desmodur® W (Covestro).

In an embodiment, the prepolymer contains at least about 10%, at leastabout 20%, at least about 22%, or at least about 24% of the isocyanate,based upon total weight of the prepolymer. In another embodiment, theprepolymer contains about 15% to about 35%, about 13% to about 32%,about 20% to about 30%, or about 22% to about 27% of the isocyanate,based upon total weight of the prepolymer.

Diols suitable as further starting materials for preparing prepolymersdisclosed herein, include at least one diol with two hydroxy groupscapable of reacting with the isocyanate and at least one carboxylic acidgroup capable of forming salt upon neutralization and incapable ofreacting with the isocyanate. Examples of diols having a carboxylic acidgroup include, but are not limited to 2,2-dimethylolpropionic acid (suchas DMPA® from GEO Specialty Chemicals and Bis-MPA from Perstorp),2,2-dimethylobutanoic acid, 2,2-dimethylovaleric acid, and DMPAinitiated caprolactones such as CAPA™ HC 1060 (Solvay). In anembodiment, the diol is DMPA.

In an embodiment, the prepolymer may contain at least about 1%, or atleast about 2.2%, or at least about 2.4% of the diol, based upon totalweight of the prepolymer. In another embodiment, the prepolymer containsabout 1.5% to about 3.5%, about 2.0% to about 3.0%, about 2.2% to about2.8%, or about 2.4% to about 2.5% of the diol, based upon total weightof the prepolymer.

The prepolymer may contain at least about 60% glycol, at least about 10%isocyanate and at least about 1% diol, based upon total weight of theprepolymer. The prepolymer may contain at least about 70% glycol, atleast about 20% isocyanate and at least about 2.2% diol, based upontotal weight of the prepolymer. The prepolymer may contain about 60% toabout 80% glycol, about 15% to about 35% isocyanate, and about 1.5% toabout 3.5% diol, based upon total weight of the prepolymer.

In an embodiment, the prepolymer further comprises a monofunctionalalcohol, such as but not limited to methanols, ethanols, propanols,butanols and 1-hexanol. The prepolymer may contain less than about 1%,less than about 0.6%, or less than about 0.5% of the monofunctionalalcohol, based upon total weight of the prepolymer. In anotherembodiment, the prepolymer contains about 0.20% to about 0.70%, about0.25% to about 0.60%, about 0.31% to about 0.55%, or about 0.31% toabout 0.51% of the monofunctional alcohol, based upon total weight ofthe prepolymer.

In an embodiment, the prepolymer further comprises 1-hexanol. Theprepolymer may contain less than about 1%, less than about 0.6%, or lessthan about 0.5% of the 1-hexanol, based upon total weight of theprepolymer. In another embodiment, the prepolymer contains about 0.20%to about 0.70%, about 0.25% to about 0.60%, about 0.31% to about 0.55%,or about 0.31% to about 0.51% of the 1-hexanol, based upon total weightof the prepolymer.

When the prepolymer contains 1-hexanol, it may comprise at least about60% glycol, at least about 10% isocyanate, at least about 1% diol andless than about 1% 1-hexanol, based upon total weight of the prepolymer.In another embodiment, the prepolymer comprises at least about 70%glycol, at least about 20% isocyanate, at least about 2.2% diol and lessthan about 0.6% 1-hexanol, based upon total weight of the prepolymer.The prepolymer may contain about 60% to about 80% glycol, about 15% toabout 35% isocyanate, about 1.5% to about 3.5% diol and about 0.20% toabout 0.70% 1-hexanol, based upon total weight of the prepolymer.

The prepolymer may be formulated to have an NCO/OH ratio, the molarratio of isocyanate groups to hydroxy groups, of about 1.30 to about2.20, about 1.30 to about 2.00, about 1.40 to about 1.90, or about 1.50to about 1.85. The NCO groups are from the isocyanate and the OH groupsare from the glycol and the diol. It was found that if the NCO/OH ratiois too low, the prepolymer viscosity will be too high to be dispersed.In addition, a low NCO/OH ratio results in low recovery ability for thefilms of the dried aqueous polyurethane dispersions disclosed herein. Onthe other hand, a NCO/OH ratio that is too high causes the films to loseelasticity or stretch elongation.

It is believed that the addition of monol in the prepolymer reduces theviscosity as it limits the molecular weight growth. To make theprepolymer dispersible, lower viscosity is preferred. In an embodiment,the viscosity is below about 3000 poises @40° C., preferably below about2500 poises @40° C. and more preferably below about 2000 poises @40° C.The viscosity may be between about 3000 to about 500 poises @40° C.,about 2500 to about 600 poises @40° C., or about 2000 to about 700poises @40° C.

The prepolymer may be formulated to have a specific Meq Acid/kg CG,where Meq is the milliequivalent of the specific functional groups, herecarboxylic acid, per kg of the prepolymer or capped glycol (CG). Thecarboxylic acid group is from a diol such as DMPA, which has two hydroxygroups capable of reacting with the diisocyanate and has one carboxylicacid group incapable of reacting with the diisocyanate. The prepolymermay be formulated to have a concentration range of the carboxylic acidgroups in milliequivalent per kg of prepolymer from about 140 to about250, about 150 to about 230, about 150 to about 220, about 155 to about220, about 170 to about 190, or about 185.

Importantly, the amount of acid in the prepolymer contributes to theviscosity of the prepolymer and the stability of the aqueous dispersionmade from the prepolymer. For example, if the concentration of acid istoo high, that means the diol concentration will be high, the prepolymerformed will have high viscosity and thus will not properly disperse intowater to form an uniform dispersion with small particle sizes. If theconcentration of acid is too low, it will not provide adequatehydrophilic sites after the neutralization, and the aqueous dispersionmade from the prepolymer will not be stable.

In an embodiment, the prepolymer may be formulated to have an NCO/OHratio of about 1.30 to about 2.00, or about 1.40 to about 1.90, and anacid concentration range of about 150 to about 220 milliequivalent perkg of prepolymer, about 155 to about 220 milliequivalent per kg ofprepolymer, or about 180 to about 190 milliequivalent per kg ofprepolymer. It was found that aqueous dispersions made from theseprepolymers have good processability and stability, and the films castfrom the aqueous dispersions made from these prepolymers have goodwhiteness retention and elasticity.

The prepolymer can be prepared by mixing the glycol, isocyanate and dioltogether in one step and by reacting at temperatures of about 50° C. toabout 100° C. for adequate time until all hydroxy groups are essentiallyconsumed and a desired % NCO of the isocyanate group is achieved.Alternatively, this prepolymer can be made by charging molten glycolinto a reactor at about 55° C. followed by addition of a DMPA solidpowder with agitation and circulation until the diol solid particles aredispersed and dissolved in the glycol. Molten isocyanate is then chargedinto the reactor with continuous agitation and the capping reaction isallowed to take place at about 90° C. for about 240 minutes, still withcontinuous agitation. The formed viscous prepolymer is then sampled todetermine the extent of the reaction by measuring the weight percentageof the isocyanate groups (% NCO) of the prepolymer through a titrationmethod. The theoretical value of the % NCO after the reaction iscompleted is 2.97 assuming the glycol MW is at 1800. If the determined %NCO value is higher than the theoretical value, the reaction should beallowed to continue until the theoretical value is reached or the % NCOnumber becomes constant. Once it is determined that the reaction iscomplete, the prepolymer temperature is maintained between 85° C. and90° C. Significantly, the prepolymers are essentially solvent free andcontain no alkyl ethoxylates or organotin catalysts. Preferred is thatthe reaction to prepare the prepolymer be carried out in amoisture-free, nitrogen-blanketed atmosphere to avoid side reactions. Noorganic solvent is added to or mixed with the starting materials before,during or after the reaction. Optionally, a catalyst may be used tofacilitate formation of the prepolymer, such as a tin-free catalyst. Forexample, K-KAT® XK-640 (King Industries Specialty Chemicals) may be usedto facilitate formation of the prepolymer.

The prepolymer of the present invention may be used to produce anaqueous polyurethane dispersion. The aqueous polyurethane dispersion maycontain about 30% to about 55%, or about 35% to about 45% prepolymer,based upon total weight of the aqueous polyurethane dispersion.

The prepolymer may be added in an amount such that the aqueouspolyurethane dispersion contains at least about 25% or at least about30% glycol, at least about 5%, or at least about 10% isocyanate, and atleast about 1% diol, based upon total weight of the aqueous polyurethanedispersion. In another embodiment, the prepolymer may be added in anamount such that the aqueous polyurethane dispersion contains about 25%to about 35% glycol, about 5% to about 15% isocyanate, and about 0.5% toabout 1.5% diol, based upon total weight of the aqueous polyurethanedispersion. In a further embodiment, the prepolymer may be added in anamount such that the aqueous polyurethane dispersion contains about 30%glycol, about 10% isocyanate, and about 1% diol, based upon total weightof the aqueous polyurethane dispersion.

The aqueous polyurethane dispersion may further contain one or more ofwater, a neutralizer, a surfactant, a defoamer, an antioxidant and athickener. The aqueous polyurethane dispersion may contain water, aneutralizer, a surfactant, a defoamer, an antioxidant and a thickener.

In an embodiment, the prepolymer, containing carboxylic acid groupsalong the polymer chains, can be dispersed with a high-speed disperserinto a de-ionized water medium that comprises: at least one neutralizingagent to form an ionic salt with the acid; at least one surface activeagent (ionic and/or non-ionic dispersant or surfactant); and,optionally, at least one diamine chain extension component.Alternatively, the neutralizing agent can be mixed with the prepolymerbefore being dispersed into the water medium. At least one antifoamand/or defoam agent and at least one rheological modifier can be addedto the water medium before, during, or after the prepolymer isdispersed.

The aqueous polyurethane dispersion may contain at least about 50%water, at least about 1% surfactant, at least about 1% thickener, lessthan about 1% neutralizer, less than about 1% antioxidant, and less thanabout 1% defoamer, based upon total weight of the aqueous polyurethanedispersion.

Water may be present in about 40% to about 60%, or about 50%, based upontotal weight of the aqueous polyurethane dispersion.

Neutralizers used in these dispersions must be capable of converting theacid groups to salt groups. Examples include, but are not limited totertiary amines (such as triethylamine (TEA), N,N-diethylmethylamine,N-methylmorpholine, N,N-diisopropylethylamine, 2-dimethylamino-2-methyl1-propanol (DMAMP) and triethanolamine) and alkali metal hydroxides(such as lithium, sodium and potassium hydroxides). Primary and/orsecondary amines may be also used as the neutralizers for the acidgroups. The degrees of neutralization are generally between about 60% toabout 140%, for example, in the range of about 80% to about 120% of theacid groups. The neutralizer may be present in about 0.5% to about 0.9%,based upon total weight of the aqueous polyurethane dispersion.

The neutralizer may comprise TEA, or may comprise TEA and a secondneutralizer. The neutralizer may comprise TEA and DMAMP.

The neutralizer may comprise DMAMP. The aqueous polyurethane dispersionmay comprise about 0.2% to about 2.0%, or about 0.5% to about 1.5% ofDMAMP, based upon total weight of the aqueous polyurethane dispersion.The aqueous polyurethane dispersion disclosed herein may be free fromTEA. “Free from,” as used herein, means that there is less than about0.01% of TEA, and preferably 0.00% of TEA, based upon total weight ofthe aqueous polyurethane dispersion. In an embodiment, the aqueouspolyurethane dispersion contains less than about 0.1% of TEA, based upontotal weight of the aqueous polyurethane dispersion.

The neutralizer may comprise DMAMP. The aqueous polyurethane dispersionmay comprise about 0.2% to about 2.0%, or about 0.5% to about 1.5% ofDMAMP, based upon total weight of the aqueous polyurethane dispersion.The aqueous polyurethane dispersion disclosed herein may be free fromTEA. “Free from,” as used herein, means that there is less than about0.01% of TEA, and preferably 0.00% of TEA, based upon total weight ofthe aqueous polyurethane dispersion. In an embodiment, the aqueouspolyurethane dispersion contains less than about 0.1% of TEA, based upontotal weight of the aqueous polyurethane dispersion.

The neutralizer may comprise DMAMP and a second neutralizer, wherein thesecond neutralizer is not TEA. The second neutralizer may be, but is notlimited to tertiary amines (other than TEA, such asN,N-diethylmethylamine, N-methylmorpholine, N,N-diisopropylethylamine,2-dimethylamino-2-methyl 1-propanol and triethanolamine), alkali metalhydroxides (such as lithium, sodium and potassium hydroxides), primary,secondary amines, or any combination thereof. When present, the aqueouspolyurethane dispersion may comprise about 0.3% to about 2.0% of DMAMP,and 0.1% to about 1.0% of a second neutralizer, based upon total weightof the aqueous polyurethane dispersion. The aqueous polyurethanedispersion may comprise about 0.5% to about 1.2% of DMAMP, and about0.2% to about 0.8% of a second neutralizer, based upon total weight ofthe aqueous polyurethane dispersion, in order to keep the degree ofneutralization in between of 60% to 140%.

Water may function as a chain extender for the prepolymer. Optionally, adiamine such as ethylenediamine (EDA) can be used a coextender.

Examples of suitable diamine chain extenders include:1,2-ethylenediamine, 1,4-butanediamine, 1,6-hexamethylenediamine,1,12-dodecanediamine, 1,2-propanediamine, 2-methyl-1,5-pentanediamine,1,2-cyclohexanediamine, 1,4-cyclohexanediamine,4,4′-methylene-bis(cyclohexylamine), isophorone diamine,2,2-dimethyl-1,3-propanediamine, meta-tetramethylxylenediamine, andJeffamine® (Texaco) of molecular weight less than 500.

Examples of surfactants include, but are not limited to, anionic,cationic, or nonionic dispersants or surfactants, such asalkyldiphenyloxide disulfonate, sodium dodecyl sulfate, sodiumdodecylbenzenesulfonate, ethoxylated nonyphenols, and lauryl pyridiniumbromide. The surfactant may be present in about 1.0% to about 5.0%,about 1.0% to about 2.0%, or about 1.0% to about 1.5%, based upon totalweight of the aqueous polyurethane dispersion.

Examples of suitable surface active agents include, but are not limitedto, anionic, cationic, or nonionic dispersants or surfactants, such assodium dodecyl sulfate, sodium dodecylbenzenesulfonate, ethoxylatednonylphenols, and lauryl pyridinium bromide.

Examples of suitable antifoaming or deforming or foam controlling agentsinclude, but are not limited to, Additive 65 and Additive 62 (siliconebased additives from Dow Corning), FoamStar® I 300 (a mineral oil based,silicone free defoamer from Cognis), mineral oils and/or silicone oilssuch as BYK 012, and Surfynol™ DF 110L (a high molecular weightacetylenic glycol non-ionic surfactant from Air Products & Chemicals).The defoamer may be present in about 0.01% to about 1.0%, about 0.1% toabout 0.5%, or about 0.1% to about 0.3%, based upon total weight of theaqueous polyurethane dispersion.

Examples of suitable rheological modifiers include, but are not limitedto, hydrophobically-modified ethoxylate urethanes (HEUR),hydrophobically-modified alkali swellable emulsions (HASE), andhydrophobically-modified hydroxy-ethyl cellulose (HMHEC).

Examples of suitable thickeners include, but are not limited to,polyurethanes such as Tafigel PUR 61 by Munzing,hydrophobically-modified ethoxylate urethanes (HEUR),hydrophobically-modified alkali swellable emulsions (HASE), andhydrophobically-modified hydroxy-ethyl cellulose (HMHEC). The thickenermay be present in about 1.0% to about 5.0%, about 1.0% to about 2.0%, orabout 1.0% to about 1.5%, based upon total weight of the aqueouspolyurethane dispersion.

Examples of antioxidants include, but are not limited to hinderedphenols such as Irganox 245 (BASF) or Cyanox 1790 (Cytec). Theantioxidant may be present in about 0.3% to about 1.0%, about 0.5% toabout 1.0%, or about 0.5% to about 0.8%, based upon total weight of theaqueous polyurethane dispersion.

Examples of a suitable polymeric component include: polyethylenimine,poly(vinylamine), poly(allylamine), and poly(amidoamine) dendrimers.

Other additives that may be optionally included in the aqueouspolyurethane dispersion or in the prepolymer include: anti-oxidants, UVstabilizers, silicones, mineral oils, colorants, pigments, delusterants,crosslinking agents, phase change materials (e.g., Outlast®,commercially available from Outlast Technologies, Boulder, Colo.),antimicrobials, minerals (e.g., copper), microencapsulated well-beingadditives (e.g., aloe vera, vitamin E gel, aloe vera, sea kelp,nicotine, caffeine, scents or aromas), nanoparticles (e.g., silica orcarbon), calcium carbonate, flame retardants, antitack additives,chlorine degradation resistant additives, vitamins, medicines,fragrances, electrically conductive additives, and/or dye-assist agents(e.g., Methacrol®, commercially available from E. I. DuPont de Nemours,Wilmington, Del.). Other additives which may be added to the prepolymeror the aqueous dispersion comprise adhesion promoters, durabilityimprovement agents, modulus modifiers, texturing agents, tackifiers,anti-static agents, anti-cratering agents, anti-crawling agents, opticalbrighteners, coalescing agents, electroconductive additives, luminescentadditives, flow and leveling agents, freeze-thaw stabilizers,lubricants, organic and inorganic fillers, preservatives, texturizingagents, thermochromic additives, insect repellants, and wetting agents,and other additives known for use by those of ordinary skill in the artto achieve desired benefits and properties.

In an embodiment, a delusterant, such as titanium dioxide, may be addedto the aqueous polyurethane dispersion. Any desired amount known in theart to impart the desired properties may be added. For example, about0.2% to about 10%, based upon total weight of the aqueous polyurethanedispersion, of the delusterant may be added.

Such optional additives may be added to the aqueous polyurethanedispersion before, during, or after the prepolymer is dispersed, as theprocess allows.

In an embodiment, the dispersion may be prepared by the addition of theprepolymer using a rotor/stator high speed disperser. The prepolymer asmade above is transferred directly into the disperser head and dispersedunder high shear forces into deionized water preferably containing atleast a surfactant, a neutralizer, an anti-oxidant and a foam controlagent. Slightly more prepolymer than required by the dispersion recipeis needed to compensate for loss in the transfer line and in thereactor. Once the addition of the prepolymer is complete, a thickenercan be added.

Aqueous polyurethane dispersions falling within the scope of the presentinvention should be expected to have a solids content of from about 10%to about 50% by weight, from about 30% to about 50% by weight, about 30%to about 45%, or about 35% to about 46%. The viscosity of aqueouspolyurethane dispersions falling within the scope of the presentinvention may be varied in a broad range from about 10 centipoises toabout 100,000 centipoises depending on the processing and applicationrequirements. For example, in one embodiment, the viscosity is in therange of about 500 centipoises to about 30,000 centipoises. Theviscosity may be varied by using an appropriate amount of thickeningagent, such as from about 0 to about 5.0 wt %, based on the total weightof the aqueous polyurethane dispersion.

The aqueous polyurethane dispersions disclosed herein have amanufacturing advantage over other dispersions, specifically those thatcontain an aromatic isocyanate, instead of an aliphatic isocyanate. Thisis due primarily to the reactivity of an aliphatic isocyanate vs. anaromatic isocyanate. The aliphatic isocyanate used in the aqueouspolyurethane dispersions disclosed herein reacts much slower when theprepolymer is dispersed in water, which allows adequate time for theviscous prepolymer to break apart into finer droplets. Thus, thedispersion has smaller and more uniform particles, which can be filteredeasily by on-line filtration system. When an aromatic isocyanate is usedinstead, the dispersion reacts quickly in water, and can cause theprepolymer droplets to solidify before breaking into small particles.This leaves large amount of grit in the dispersion, which requiresoff-line filtration with reduced yield and productivity.

It has been found that upon drying, the dried aqueous polyurethanedispersion of the present invention may form a continuous elastic filmwith high stretch and recovery. Given that the films and fabrics areporous materials, it is recognized that the film or dispersion maypartially or completely impregnate the fabric of the shaping article.For example, the dried aqueous polyurethane dispersion may form a layerwhich is partially separate from the surrounding layers, or may becompletely transferred to the surrounding layer or layers to form anintegrated article without a distinguishably separate film layer.

Further, the aqueous polyurethane dispersion is resistant to yellowingand hydrolysis. In particular, the aqueous polyurethane dispersion ofthe present invention, and shaped articles made therefrom, has beenfound to have improved whiteness retention (also referred to as improvedresistance to oxidative discoloring (or yellowing)) as compared to otherfilms or articles made from other dispersions known in the art, such asthose containing an aromatic isocyanate. This is particularly importantfor consumer goods as yellowing or discoloration is particularlyobjectionable for garments and consumer goods.

A CIE whiteness index value is a whiteness measurement standarddeveloped by the French-based International Commission on Illumination(also abbreviated as CIE) using D65 illumination representing outdoordaylight. Whiteness retention is a measurement of resistance to changein color after treatment or exposure, measured by the change in the CIEwhiteness index value over time. Thus, improved whiteness retention of afabric means that it has a greater resistance to change in color. Asused herein and unless otherwise specified, the CIE whiteness indexvalue (absolute value) is understood as that of a sample without a coloreffecting additive, such as a pigment, colorant, brightener, dye, or thelike. One of ordinary skill in the art understands that such additivescould be added to an aqueous polyurethane dispersion or shaped articlewhich would alter the absolute value of the CIE whiteness index.

A shaped article, e.g., a film, coated on a Mylar® polyester sheetsubstrate and formed from the aqueous polyurethane dispersions disclosedherein may have a CIE whiteness index value of about 50 to about 60.After thermal exposure (exposure in a thermal chamber to heated air at195° C. for five minutes), the film may have a CIE whiteness index valueof about 30 to about 40. That is a reduction in CIE whiteness indexvalue of less than about 20 index points, otherwise understood as areduction in whiteness of about 30% to about 40%. After UV exposure(using, e.g., a Xenon Arc lamp simulating exposure to daylight,including UV) for 8 hours, the film may have a CIE of about 50 to about60. That is no reduction in CIE whiteness index value after UV exposure,i.e., less than about 2%, or about 0%. After exposure to NO₂ (24 hours),the film may have a CIE whiteness index value of about 48 to about 58,and a reduction in CIE whiteness index value of about 0 to 3 indexpoints. That is a reduction in CIE whiteness value of less than about5%, or about 0% to about 4%.

In addition, the film formed from a dried aqueous polyurethanedispersion disclosed herein has improved tensile properties over filmsmade from other dispersions. The film may have a tensile strength (whenthe film is stretched in the sixth cycle) of over about 0.14 g/denier,or over about 0.15 g/denier. The film may have a tensile strength ofabout 0.14 g/denier to about 0.24 g/denier, or about 0.15 g/denier toabout 0.22 g/denier. It was found that higher tensile strengths arepossible when the NCO/OH ratio of the prepolymer, or aqueouspolyurethane dispersion, is between about 1.50 and about 1.90, with thepolymer number average molecular weight larger than 10,000. An NCO/OHratio lower than about 1.5 produces films that have less or inadequatepower (stretch/recovery), and an NCO/OH ratio higher than about 1.9produces films that are brittle and have reduced elongation (ELO).

In an embodiment, the film formed from a dried aqueous polyurethanedispersion having NCO/OH ratio of about 1.50 to about 1.90, may have atensile strength of about 0.14 g/denier to about 0.24 g/denier, or about0.15 g/denier to about 0.22 g/denier. That aqueous polyurethanedispersion may also have a milliequivalent carboxylic acid per kg ofprepolymer of about 150 to about 220, about 155 to about 220, or about180 to about 190.

In an embodiment, a single layer of a fabric or foam may be folded tofoam two or more layers of the multiple layer article with a film oraqueous polyurethane dispersion as an intermediate layer (where the filmmay be considered ‘embedded’ within the article). In this embodiment,the article may then also be molded or pressed to a desired shape, suchas for a body shaping garment. Single-layer and multi-layered articlesmay be molded. Molded and non-molded articles may have different levelsof stretch and recovery. The molded articles may comprise a body shapingor body supporting garment, such as a brassiere, sports bra or bralette.Where a film is placed at the point of folding, it may provideadditional stretch recovery power, such as at a hem or for a bodyshaping garment, and additional support. This is also useful in agarment such as an underbust bra where the film/tape placement mayprovide increased wall strength or rigidity and may keep the garmentfrom rolling at the edge. The film may also be placed at the point wherethe edges of the single layer meet which form the double layer fabric asshown in FIG. 16 which is described hereinbelow in more detail.Additional fabric or foam layers may also be included within the foldedover layer as desired. For example, a fabric layer may be folded over toform two layers where a film and a foam are included within the foldedarea.

In an embodiment, the film may kiln an external layer. Including thefilm on an external surface forms many advantageous functions. Forexample, the film may provide an anchor or area of increased friction toreduce the relative movement between the fabric laminate and an externalsubstrate. This is particularly useful when the article is anundergarment including a skin-contacting surface (where the wearer'sskin is the substrate). Alternatively, the substrate may be outerclothing which is in contact with the fabric laminate of the inventivearticle. Where the substrate is outer clothing of a wearer and thearticle is worn as an undergarment, the article prevents or reduces therelative movement of the outer garment. In addition, an outer garment(e.g. a dress) may include an inventive film to maintain the relativeplacement of an inner garment (e.g., a slip).

After the layers of fabric, foam, and the film have been selected, theymay subsequently be adhered through pressing or molding to form flat orshaped articles (including articles having three-dimensions such as amolded breast cup). The processes to prepare the pressed and moldedarticles of some embodiments include the use of pressure and heat asnecessary. For example, heat may be applied at about 150° C. to about200° C. or about 180° C. to about 190° C., including about 185° C. for asufficient time to achieve a molded article. Suitable times forapplication of heat include, but are not limited to, from about 30 secto about 360 see including from about 45 sec to about 120 sec. Bondingmay be effected by any known method, including but not limited to,microwave, infrared, conduction, ultrasonic, pressure application overtime (i.e. clamping) and combinations thereof. With the application ofheat and pressure to the articles including films or aqueouspolyurethane dispersions, and given that films and fabrics arethemselves porous materials, it is recognized that the film ordispersion may partially or completely impregnate the fabric or foam ofthe article.

After application of the inventive aqueous polyurethane dispersion orfilm, the garment may exhibit improved moisture transport, comfort, andlighter weight and feel (e.g., when sew-in panels are eliminated) whencompared to conventional garments of the same type that do notincorporate the aqueous polyurethane dispersion or shaped article. Inaddition, unlike some conventional garments that have extra seams,panels sewn-in or bonded, and/or layers of material to create improvedhold, the aqueous polyurethane dispersion or shaped article of thepresent disclosure may be applied directly to the fabric or material ofthe garment to create the hold, thereby eliminating the need for extraseams, panels and material.

An article of the present invention may be a body-shaping garment, suchas bust supporting garment, including a brassiere, bralette or sportsbra, other women's undergarment, and men's undergarment. These articlescan provide the desirable features of body shaping and support whilestill providing comfort, breathability, air permeability, moisture/vaportransport, wicking, and combinations thereof. In an article of anembodiment of the present invention, the layers of fabric and film maytake on predetermined shapes and may be arranged in predeterminedorientations relative to each other in the design of a molded or shapedarticle such as the cups of a brassiere construction. The layers may beused either alone or in combination with other materials that are sewn,glued or otherwise applied to the fabrics.

In some embodiments there is a system for the construction of a garmentwith integrated shaping ability provided by the fabric. This system ofconstruction may be used in a variety of different garment constructionssuch as activewear, sportswear, men's and women's intimate apparel suchas bras, underwear, panties, shaping garments, legwear and hosiery suchas pantyhose, ready-to-wear garments such as denim jeans, camisoles,tailored shirts, and pants among others. This construction may beapplied to any formable body area. While many advantages of the fabricconstructions are included, it is further recognized that the utility isnot limited to garments, but also finds applicability with any shapableor formable medium, including cushions for furniture which are alsosubject to movement and potential slipping of a fabric in contact withthe shapable area.

In order to add additional support and other features, the filmcomposition may be added to different areas of the article. For example,it may either extend through the entire area of the article or to aselected portion to provide different benefits. For example, a bustsupporting garment, such as a brassiere, bralette or sports bra, mayinclude a film applied in the cup portion. In the cup, it can be usefulto use a portion of film in the lower periphery of the cup for support,in a central portion of the cup for modesty, in the side periphery forshaping, and/or in specific areas for embellishment or decoration. Inanother embodiment, the film may be applied in the lower peripheries ofthe cup of a bust supporting garment for support, in a central portionfor modesty, in the side peripheries for shaping, in the wing portions,or any combination thereof. Any number of combinations of applicationsare possible to provide the desired shaping or support.

In an embodiment, the aqueous polyurethane dispersion or film may beapplied to swimwear, active wear or shapers in the bust, belly, thighs,seat, or any combination thereof. In another embodiment, the aqueouspolyurethane dispersion or shaped article may be applied to active wearor shapers in the calf, arms, chest, bust, belly, thighs, seat, or anycombination thereof. It has been found that a small amount of theaqueous polyurethane dispersion selectively placed and applied ongarments leads to significant affects and results on the human body(e.g., in terms of shape, comfort and/or support) in those areas towhich the aqueous polyurethane dispersion has been applied.

When the aqueous polyurethane dispersion or shaped article is applied toswimwear, the swimwear exhibits improved chlorine resistance.Surprisingly, the improved chlorine resistance of the swimwear isachieved without incorporating additives that are known in the art toimprove chlorine resistance, such as a mineral additive being a mixtureof huntite and hydromagnesite, as disclosed in U.S. Pat. No. 5,626,960,which is incorporated by reference herein in its entirety. Without beinglimited to a theory, it is believed that improved chlorine resistance isachieved because the inventive film breaks down and wears away slowly.Additionally, after exposure to a chlorinated environment, the hold (orfabric retractive force due to elastic properties of the applieddispersion) and altered stress profile of the garment where the aqueouspolyurethane dispersion or shaped article has been applied remainssubstantially constant, even after about 30, about 40, about 60, about100, about 180 or about 200 hours in a chlorinated environment. Thechlorinated environment may have a pH of about 7.5, a chlorineconcentration of about 3.5 ppm, and a temperature of about 25° C.Substantially constant means that percentage change in the fabricmodulus to a 40% stretch is not reduced more than about 15%, or about10%, after an initial decrease in the first ten hours to the specifiedtime. While the absolute value of the force required to stretch thetreated fabric (which also may be referred to as modulus boost or hold)decreases over time, it decreases at approximately the same rate as theunderlying fabric. Therefore, the hold remains approximately constant.

After 220 hours in a chlorinated environment, the hold (or gram-force ofthe fabric strength) was surprisingly shown to decrease at a rate equalto that of the chlorine resistant protected spandex in the underlyingfabric. This occurs despite the fact that the aqueous polyurethanedispersion does not contain any additives known to the industry toprotect segmented polyurethanes, such as spandex. Of course, it is knownto one of ordinary skill in the art that chlorine resistance may beotherwise enhanced by adding known additives that impart said property.

It is understood that the swimwear discussed in relation to improvedchlorine resistance is made from fabric that is of good quality andremains intact after 220 hours in a chlorinated environment.

In the figures of the disclosure, the films are shown as a separatelayer for clarity only. As explained above, the film on attachment maypartially or completely fill the pores of the fabric or foam substrate.

In FIGS. 1-3, 8-9, and 14-15, a portion of fabric is shown having asubstantially trapezoidal shape. Such a shape is useful as a bra wingportion, as discussed. However, although referred to a a bra wingportion, the fabric portion may be useful in other areas of a garmentand is shown to demonstrate an example of how a film may be orientedwith respect to the shape of the fabric to alter the stress-profile ofthe fabric. A variety of geometric shapes for both the fabric portionand the film portion are contemplated and can be chosen based on thedesired alteration of stress-profile. The alteration may be to providecomfort by distributing stress throughout the garment or to increasestress in portions of the garment to provide additional control orsupport.

As shown in FIG. 1, a film composition 2 may be geometrically invertedonto a portion of a garment such as a bra wing portion 1, which is asubstantially trapezoid shape, and is shown as a trapezoid. The corners4 that overlap extend beyond the edges of the wing portion may be foldedover or cut to shape of the film.

As an alternative, FIG. 2 also shows a film composition 2 that has beengeometrically inverted onto a wing portion 1, however, while the filmhas substantially the same shape as the wing portion, it is reduced insize to avoid the overlapping corners 4 of FIG. 1, while still providingan altered stress profile.

In either FIG. 1 or FIG. 2, the fabric section 1 may be a wing includinga trapezoid having a wide end and a short end. The film 2 also has awide and a short end. The short end of the film is placed correspondingto the wide end of the fabric section and the wide end of the film isplaced corresponding to the shorter end of the fabric section.

FIG. 8 and FIG. 9 also show fabric portions 1 having a film region 2bonded to the fabric portion 1. In each of FIG. 8 and FIG. 9, the filmregion has a triangular shape.

As shown in FIG. 3, another method of altering the stress profile of agarment, such as a wing 1 is to include a narrow strip of a film 2.Although this film shown appears substantially linear, it is understoodthat this may be modified to a non-linear shape depending on the mannerof altering the stress profile that is selected. The film 2 may extendto the edges of the wing 1 as shown or may alternatively begin and endat intermediate portions of the wing 1. The film 2, may be orientedalong a diagonal (as it appears in FIG. 3) or may be perpendicular tothe wing edge.

In other words, the fabric section may have a top portion anintermediate portion and a bottom portion where the film is orientedadjacent to two or more portions of the fabric section. The film may beoriented along a diagonal from the top of the fabric section to thebottom of the fabric section, along a diagonal at other portions withinthe fabric or perpendicular to the fabric section.

FIG. 4 shows a brassiere as an example of a garment that can include thefilm to alter the garment's stress profile. The brassiere includes awing portion 1 and two breast cup portions 6 and 10. The cup portion 6includes a film 8 located along the bottom periphery of the cup 6. Theother cup portion 10 includes a film that is located along the sideperiphery 12. The side periphery film 12 and the bottom periphery film 8can be used together or separately to adjust the stress profile of thegarment to provide shaping and support. Although a brassiere is shown asthe example, it is understood that this could apply to other formableareas of the body, such as the derriere (also referred to as the seat),the thighs, or the belly.

FIG. 5 also shows a brassiere including an underwire portion 18. Theunderwire portion is also a potential cause of a pressure point in abrassiere. The addition of films 14 and 16 can provide one or both ofadditional comfort and support by altering the stress profile to whichthe underwire portion 18 contributes.

Although the brassieres of FIGS. 4-7 appear to be back closurebrassieres that include straps, it is understood that straps areoptional, that a front closure (not shown) may be included in the areabetween the breast cups at 14, and that the brassieres may or may notinclude a bridge between the cups.

The brassiere of FIG. 6 includes two breast cup portions 20 each havinga film portion 22 at the inner part of the cup. The stress profile ofthe cup portions 20 are altered by including the film portions 22 whichmay vary in width from the top part of the cup 24 which is wider asshown as the film portion 22 extends to the inner part of the cup 26.The opposite configuration is shown in FIG. 7, where the cup portions 20include film portions 28 that vary in width from a narrow part at thetop of the cup 30 extending to the bottom inner part of the cup 32.Altering the stress profile of this area of the brassiere can avoidpinch points while provide support or enhancement as desired. In orderto achieve the desired effect, other geometries or configurations of thefilm portions 22 and 28 are contemplated.

FIG. 10 and FIG. 11 each show a panty 34 including different filmportions 36, 37, 38 and 40. The film region 36 can be located at thewaistband as shown in FIG. 10 to provide the garment with a reducedstress profile to reduce the appearance of the waistband throughclothing. The width of the film 36 can vary in the front or back of thegarment to reduce pressure providing a pinch point or alter the stressprofile to increase support (such as by providing tummy control).Similarly, the film portions at the leg bands 36 and 37 can vary inwidth to provide distribution of stress along the back portiondecreasing a pinch point that can show as a panty line under clothing,such as by increasing the width of the film along the back portion 37.FIG. 11 includes a film region 40 of a different geometry that canprovide additional control, such as tummy control, or by providingsupport useful for maternity panties.

Any of the film regions 1 may be included on a single surface 2 as shownin FIG. 12 where the surface 2 may be either a fabric, foam or othersubstrate suitable for a garment. Alternatively, the film 2 may beincluded between two surfaces such as a fabric, foam, etc. as in FIG. 13where a top surface layer 1 and bottom surface layer 3 are included.

FIG. 14 and FIG. 15 show two possibilities for using a folded overfabric that provides a top surface layer 1 and a bottom surface layer 2after folding along a preselected folding lines 42. Arrows show thedirection of folding in FIG. 14 and FIG. 15. The edges of the bottomsurface layers 3 meet to form a butt seam 5 as shown in FIG. 14A andFIG. 15A. The edges 5 may be attached or bonded to the film region 2 atthat point.

FIG. 16 is a cross-section of a butt seam at line X-X as indicated inFIG. 14A. The seam 5 indicates the edges of the fabric or othersubstrate that is folded over and bonded or attached. The film region 2may be bonded to the top surface 1, the bottom surface 3 or two both thetop and bottom surfaces. The folded portion 42 is indicated todemonstrate the orientation of layer prior to bonding, however, wherethe fabric is sufficiently thin, the cross-section will appearsubstantially linear. Also, a space 44 is shown to demonstrate that thebonded film 2 may not extend to the folded portion 42 of the fabric,however, this space 44 may be absent depending on the bonding techniquebecause the film may melt and fill this available space.

In an embodiment, the film may act as an adhesive to attach two or morelayers of fabric or foam, or to attach a layer of fabric to foam. Onesuitable method for accomplishing this is to apply the inventive aqueouspolyurethane dispersion to a layer of fabric or foam by any suitablemethod. Methods for applying the aqueous polyurethane dispersion includespraying, kissing, printing, brushing, dipping, padding, dispensing,metering, painting, and combinations thereof. This may be followed byapplication of heat and/or pressure.

Optionally, in an embodiment, an adhesive may be used to attach a filmto a fabric or foam layer. Examples of suitable adhesives include, butare not limited to, thermoset or thermoplastic adhesives, pressuresensitive adhesives, hot melt adhesives, and combinations thereof. Theadhesive may be used to adhere layers and may be applied to any of thefabric, foam, fabric laminate or film. The inventive aqueouspolyurethane dispersion may also be used as an adhesive to adhere morethan one layer of any fabric, foam or film as described in someembodiments. Alternatively, the film may be sewn into a garment.

As described above, there are a variety of fabric constructions that areuseful for the articles of the present invention. In addition, the driedaqueous polyurethane dispersion may provide structural properties,flexibility, adhesion, or any combination of these. The order of layerarrangement may be (1) fabric layer, foam layer, aqueous polyurethanedispersion layer; (2) fabric layer, foam layer, aqueous polyurethanedispersion layer, foam layer, fabric layer; (3) fabric layer, aqueouspolyurethane dispersion layer, fabric layer; (4) foam layer, aqueouspolyurethane dispersion layer, foam layer; (5) foam layer, aqueouspolyurethane dispersion layer; (6) fabric layer, aqueous polyurethanedispersion layer; or any combination of these which may be combined toachieve more layers in the fabric construction. An adhesive may beincluded to adhere any of the layers, including wherein the aqueouspolyurethane dispersion composition is the adhesive.

In an embodiment, no organic solvents are added to the dispersion. Inanother embodiment, an organic solvent may be used in the preparation ofa film or dispersion. An organic solvent may be used to lower theviscosity of the prepolymer through dissolution and dilution and/or toassist the dispersion of solid particles of the diol compound having acarboxylic acid group such as 2,2-dimethylolpropionic acid (DMPA) toenhance the dispersion quality. It may also serve for the purposes toimprove the film uniformity such as reducing streaks and cracks in thecoating process.

An organic solvent suitable for use herein is substantially orcompletely non-reactive to isocyanate groups, stable in water, and has agood solubilizing ability for DMPA, the formed salt of DMPA andtriethylamine, and the prepolymer. Examples of suitable solvents includeN-methylpyrrolidone, N-ethylpyrrolidone, dipropylene glycol dimethylether, propylene glycol n-butyl ether acetate, N,N-dimethylacetamide,N,N-dimethylformamide, 2-propanone (acetone) and 2-butanone(methylethylketone or MEK).

When used, the amount of organic solvent added to the film or dispersionvaries. The organic solvent may be included in amounts of less than 50%by weight of the dispersion. Smaller amounts may also be used such asless than 20% by weight of the dispersion, less than 10% by weight ofthe dispersion, less than 5% by weight of the dispersion, or less than3% by weight of the dispersion.

The inventive aqueous polyurethane dispersions are particularly suitablefor adhesive films, which can be used for fabric bonding, lamination,and adhesion purposes when applied with heat and pressure for arelatively short period of time. Pressures, can for example, range fromabout atmospheric pressure to about 60 psi and times can range from lessthan about one second to about 30 minutes in accordance with the bondingmethod used.

Some films of dried aqueous polyurethane dispersions may be made bycoating the dispersion onto a release paper and drying to remove waterat temperatures below about 100° C. through commercially availableprocesses to form a film on the paper. The resulting film sheets can beslit into strips of desired width and wound-up into spools for later usein applications to form stretch articles, for example textile fabrics.Examples of such applications include: stitch-less or seamless garmentconstructions; seam seal and reinforcement; labels and patches bondingto garments; and localized stretch/recovery enhancement. The adhesionbonding can be developed in the temperature range of from about 100° C.to about 200° C., such as from about 130° C. to about 200° C., forexample, from about 140° C. to about 180° C., in a period of 0.1 secondsto several minutes, for example, less than about one minute. Typicalbonding machines include Sew Free (commercially available fromSewSystems in Leicester, England), Macpi hemming machine (commerciallyavailable from the Macpi Group in Brescia, Italy), Framis hot airwelding machine (commercially available from Framis Italy, s p.a. inMilano, Italy). This bonding is expected to be strong and durable whenexposed to repeated wear, wash, and stretch in a textile fabric garment.

The coating, dispersion, or shaped article may be pigmented or coloredand also may be used as a design element.

The aqueous polyurethane dispersion can be used alone or with otheraqueous dispersions of a different polymer. Further, the aqueouspolyurethane dispersion can be cross-linked with selected crosslinkingagents, including, e.g., polycarbodiimides and polyisocyanates.

The aqueous polyurethane dispersion may be diluted to a desired solidcontent prior to application to the substrate. The substrate to whichthe aqueous polyurethane dispersion is applied may be a textile fabricor a nonwoven material.

The aqueous polyurethane dispersion can be applied directly to thesubstrate and/or dried as a film, a tape or in various selected patternssuch as, but not limited to, dots, shapes such as triangles, circles,and rectangles, zigzags and/or lines depending upon where stretch andrecovery is desired. When applied in zigzags or in non-parallel ordiscontinuous lines, it is possible to manipulate the directionality orintensity (or both) of the changes in elastic modulus. Additionalbenefits include improved visual design aesthetic (owing to the shape ofthe applied patterns as well as the ability to add colorant, reflective,or other additives) and ability to manipulate the fabric drape andtactility. For example, while a solid continuous panel may createmaximum increase in modulus, it may feel stiff or papery or noisy whenhandled. Using interrupted, discontinuous, or broken patterns canalleviate the stiff and papery feel in addition to changing the modulus.

In addition, articles with films laminated thereon or aqueouspolyurethane dispersions applied thereto can be molded. For example,fabric can be molded under conditions appropriate for the hard yarn inthe fabric. Also, molding may be possible at temperature which will moldthe fabric laminate or aqueous polyurethane dispersion, but belowtemperatures suitable for molding the hard yarn.

One suitable method of attaching a layer of film to a substrate islamination using any method wherein heat or energy is applied to thefilm. Methods of heat application include, for example, ultrasonic,direct heat, indirect heat, and microwave.

Methods and means for applying the films of some embodiments include,but are not limited to: roll coating (including reverse roll coating);use of a metal tool or knife blade (for example, pouring a dispersiononto a substrate and then casting the dispersion into uniform thicknessby spreading it across the substrate using a metal tool, such as a knifeblade); spraying (for example, using a pump spray bottle); dipping;painting; printing; stamping; and impregnating the article. Thesemethods can be used to apply dispersion directly onto a substratewithout application of additional adhesive materials and may be repeatedif additional/heavier layers are required. The dispersions may beapplied to any fabrics of knits, wovens or nonwovens made fromsynthetic, natural, or synthetic/natural blended materials for coating,bonding, lamination and adhesion purposes. The water in the dispersioncan be eliminated with drying during the processing (for example, viaair drying or use of an oven), leaving the precipitated and coalescedpolyurethane layer on the fabrics to form an adhesive bond.

At least one coagulant may optionally be used to control or to minimizepenetration of an aqueous polyurethane dispersion into a fabric or otherarticle. Examples of coagulants that may be used include calcium nitrate(including calcium nitrate tetrahydrate), calcium chloride, aluminumsulfate (hydrated), magnesium acetate, zinc chloride (hydrated) and zincnitrate.

A tool, such as a knife, may be used for applying a film or an aqueouspolyurethane dispersion to a fabric. The knife blade can be made ofmetal or any other suitable material. The knife blade can have a gap ofa predetermined width and thickness. The gap may range in thickness, forexample, from 0.2 mils to 50 mils, such as a thickness of 5 mils, 10mils, 15 mils, 25 mils, 30 mils, or 45 mils.

The thickness of a film or an aqueous polyurethane dispersion applied toa substrate may vary depending on the application. In the case of a film(that is, a dried aqueous polyurethane dispersion), the final thicknessmay, for example, range from about 0.1 mil to about 250 mil, from about0.5 mil to about 25 mil, from about 0.5 mil to about 12 mil, from about0.5 mil to about 10 mil, from about 1 to about 9 mil, or from about 1.5mil to about 6 mil (one mil=one thousandth of an inch).

For an aqueous polyurethane dispersion, the amount applied to asubstrate may, for example, range from about 2.5 g/m2 to about 6.40kg/m2, from about 12.7 kg/m2 to about 635 g/m2, or from about 25.4 kg/m2to about 152.4 g/m2.

Films and aqueous polyurethane dispersions of the disclosure may beapplied to a fabric (woven and nonwoven), as well as to leather (real orsynthetic), paper, metal, plastic, and scrim. End products that can beproduced using the aqueous polyurethane dispersions and films in thisdisclosure include, but are not limited to: apparel, which includes anytype of garment or article of clothing; knitted gloves; upholstery; hairaccessories; bed sheets; carpet and carpet backing; conveyor belts;medical applications, such as stretch bandages; personal care items,including incontinence and feminine hygiene products; and footwear.Also, an article may be coated with an aqueous polyurethane dispersionor covered with a film and be used as a sound suppression article.Non-elastic fabrics incorporating an aqueous polyurethane dispersion orfilm can have improved stretch and recovery, and improved moldingproperties.

Accordingly, the aqueous polyurethane dispersions and methods for theirapplication are particularly useful in production of articles whereinstretch and recovery is desired, in whole or in part. These articles canprovide the added effect of body shaping and support while providingcomfort. The article may be a garment.

Examples of garments that can be produced using the dispersions andmethods falling within the scope of the present invention, include butare not limited to: disposable undergarments, brassieres, bralettes,panties, lingerie, swimwear, shapers, camisoles, hosiery, sleepwear,aprons, wetsuits, ties, scrubs, space suits, uniforms, hats, garters,sweatbands, belts, activewear, outerwear, rainwear, cold-weatherjackets, pants (including denim jeans), shirtings, dresses, blouses,mens and womens tops, sweaters, corsets, vests, knickers, socks, kneehighs, dresses, blouses, aprons, tuxedos, bisht, abaya, hijab, jilbab,thoub, burka, cape, costumes, diving suit, kilt, kimono, jerseys, gowns,protective clothing, sari, sarong, skirts, spats, stola, suits,straitjacket, toga, tights, towel, uniform, veils, wetsuit, medicalcompression garments, bandages, suit interlinings, waistbands, and allcomponents therein. In certain embodiments, the garment is a brassiere,a bralette, swimwear (for men or women), shapers or activewear(including leggings, sports bras, shorts and tops).

The aqueous polyurethane dispersion or film may be applied in apredetermined shape and/or to a selected area of a garment.Alternatively, the aqueous polyurethane dispersion or film may beapplied into the whole of a garment. The aqueous polyurethane dispersionor film may be applied to a seam or support area of the garment.

After application of the aqueous polyurethane dispersion or shapedarticle, the garment may exhibit improved moisture transport, comfort,and lighter weight and feel (e.g., when sew-in panels are eliminated)when compared to conventional garments of the same type that do notincorporate the aqueous polyurethane dispersion or shaped article. Inaddition, unlike some conventional garments that have extra seams,panels sewn-in or bonded, and/or layers of material to create improvedhold, the aqueous polyurethane dispersion or shaped article of thepresent disclosure may be applied directly to the fabric or material ofthe garment to create the hold, thereby eliminating the need for extraseams, panels and material.

The following examples are meant to be exemplary and not limiting of theembodiments described herein.

EXAMPLES

Representative embodiments of the present invention will be describedwith reference to the following examples that illustrate the principlesand practice of the present invention. In no way is the scope of theinvention limited to these representative embodiments. In theseexamples, the following raw materials were used:

TABLE 1 Ingredient Chemical Name CAS # Tradename Vendor Glycol PTMEG25190-06-1 Terathane ® INVISTA 1800 Isocyanate Dicyclohexylmethane5124-30-1 Vestanate Evonik diisocyanate H12MDI DMPA Dimethylolpropionic4767-03-7 D-MPA GEO Acid Neutralizer Triethylamine 121-44-8 TEA BASFSurfactant Alkyldiphenyloxide 119345-04-9 Dowfax 2A1 Dow DisulfonateDefoamer mineral oil, silicone Mixture BYK 012 BYK Additives oil &Instruments Antioxidant hindered phenols 36443-68-2 Irganox 245 BASFThickener polyurethane mixture Tafigel PUR Munzing 61

The following analytical methods were used in the Examples below wherenoted: 1) Titration methods; 2) Microwave methods; 3) BrookfieldViscosity, RV Spindle methods #3/10 rpm @ 25° C.

The titration method used for determining the percent isocyanate (% NCO)of the capped glycol prepolymer was carried out according to the methodof S. Siggia, “Quantitative Organic Analysis via Functional Group,” 3rdEd., Wiley & Sons, New York, pages 559-561 (1963), using apotentiometric titration. The dispersion solid concentration wasdetermined by a microwave solids analyzer LABWAVE 9000. The dispersionviscosity was determined with a Brookfield Viscometer.

Example 1 Prepolymer Preparation without 1-Hexanol

A polyurethane prepolymer was made using a polytetramethylene etherglycol, an aliphatic diisocyanate such as PICM (4,4′-methylene bis(cyclohexyl isocyanate), a hydrogenated version of 4,4′-MDI) and a diolcontaining a sterically hindered carboxylic acid group. Morespecifically, the following ingredients and unit quantities were used tomake the prepolymer:

TABLE 2 Ingredient CAS Number Unit Quantity Terathane* 1800 251090-06-172.7806 1-Hexanol 111-27-3 0.0000 Vestanat* H12MDI 5124-30-1 24.7380DMPA 4767-03-7 2.4814 Prepolymer total 100.0000

The reaction to prepare the prepolymer was carried out in amoisture-free, nitrogen-blanketed atmosphere to avoid side reactions.

In this example, a 30 gallon reactor, jacketed with hot water andequipped with an agitator, was used. This reactor was heated to atemperature of about 55° C. A pre-determined weight of molten Terathane®1800 glycol was charged into the reactor. Then, DMPA solid powder wasadded to the reactor with agitation and circulation, under nitrogenblanket, until the DMPA solid particles were dispersed and dissolved inglycol.

Molten PICM was then charged into the reactor with continuous agitationand the capping reaction was allowed to take place at 90° C. for 240minutes, still with continuous agitation. The formed viscous prepolymerwas then sampled to determine the extent of the reaction by measuringthe weight percentage of the isocyanate groups (% NCO) of the prepolymerthrough a titration method. The theoretical value of the % NCO after thereaction is completed is 2.97 assuming the glycol MW is at 1800. If thedetermined % NCO value is higher than the theoretical value, thereaction should be allowed to continue until the theoretical value isreached or the % NCO number becomes constant. Once it was determinedthat the reaction is complete, the prepolymer temperature was maintainedbetween 85 and 90° C.

Example 2 Preparation of Aqueous Polymer Dispersion with Prepolymer ofExample 1

The dispersion was prepared by the addition of the prepolymer of Example1 using a rotor/stator high speed disperser. The prepolymer as made inExample 1 was transferred directly into the disperser head and dispersedunder high shear forces into deionized water, containing a surfactant, aneutralizer, an anti-oxidant and a foam control agent. Slightly moreprepolymer than required by the dispersion recipe was needed tocompensate for loss in the transfer line and in the reactor.

The ingredients for making the dispersion and the composition of thedispersion are shown below in Table 3.

TABLE 3 Ingredient CAS Number Unit Quantity Terathane* 1800 251090-06-130.1391 Vestanat* H12MDI 5124-30-1 10.2442 DMPA 4767-03-7 1.02761-Hexanol 111-27-3 0.0000 DI Water 7732-18-5 54.8093 Dowfax 2A1119345-04-9 1.2652 Triethylamine 121-44-8 0.7830 Irganox 245 36443-68-20.6051 Tafigel PUR 61 Mixture 1.0000 BYK 012 Mixture 0.1265 Other 0.0000Total 100.0000

In making a typical batch of 100 kg of the aqueous polymer dispersion,Dowfax 2A1 surfactant (1.2652 kg), an anti-oxidizer Irganox 245 (0.6051kg), and foam control agent BYK-012 (0.1265 kg) were mixed and dissolvedin the deionized water (54.8093 kg). The triethylamine neutralizer(0.783 kg) was added to the above water mixture 5 minutes prior to theaddition of the prepolymer. The prepolymer (41.4109 kg) maintained at atemperature between 85 and 90° C. was added into the water mixture withhigh speed dispersing. The addition rate (typically at about 1.5 kg/minor about 30 minutes) of the prepolymer should be controlled to allow theformation of uniform dispersion, and the temperature of the dispersionshould be kept between 40 and 45° C. Once the addition of prepolymer wascomplete, mixing was continued for 60 minutes. Then, a thickener TafigelPUR 61 (1.00 kg) was added and allowed to mix for another 60 minutes.The as-made dispersion was continuously agitated at low speed for 8hours (or overnight) in the container to eliminate foams and to ensurethe reaction had reached completion. The finished dispersion typicallycontains about 42% solids, with viscosity about 4000 centipoises and pHin the range of 7.0 to 8.5.

The dispersion was then filtered through 100 micron bag filters toremove big particles before packed for shipment. It is recommended touse 55 gallon metal drums with polyethylene liner inside to contain thedispersion for shipment.

Final product specifications were determined as shown in Table 4.

TABLE 4 Parameters Aim ±Limits Method Prepolymer % NCO* 3.00 0.10Titration Dispersion Solids, % 44.0 2.0 Microwave Dispersion Viscosity,RV Spindle #3/10 cps** 4000 1000 rpm@25° C. Dispersion pH 7.7 0.7Dispersion Filterability Passing through filter bags no more than 100microns *Sampled 20-30 minutes before the prepolymer is dispersed.**Sampled and measured 24 hours after the dispersion is thickened.

Example 3 Preparation of Prepolymer with 1-Hexanol

The polyurethane prepolymer was made using a polytetramethylene etherglycol, 1-Hexanol, an aliphatic diisocyanate such as PICM(4,4′-methylene bis (cyclohexyl isocyanate), a hydrogenated version of4,4′-MDI) and a diol containing a sterically hindered carboxylic acidgroup. Table 5 lists the ingredients and unit quantities used to makethe prepolymer.

TABLE 5 Ingredient CAS Number Unit Quantity Terathane* 1800 251090-06-172.4492 1-Hexanol 111-27-3 0.4087 Vestanat* H12MDI 5124-30-1 24.6607DMPA 4767-03-7 2.4814 Prepolymer total 100.0000

The reaction to prepare the prepolymer was carried out in amoisture-free, nitrogen-blanketed atmosphere to avoid side reactions.

In this example, a 30 gallon reactor, jacketed with hot water andequipped with an agitator, was used. This reactor was heated to atemperature of about 55° C. A pre-determined weight of molten Terathane®1800 glycol was charged into the reactor. The 1-Hexanol was addedsecond. Then, DMPA solid powder was added to the reactor with agitationand circulation, under nitrogen blanket, until the DMPA solid particleswere dispersed and dissolved in glycol.

Molten PICM was then charged into the reactor with continuous agitationand the capping reaction was allowed to take place at 90° C. for 240minutes, still with continuous agitation. The formed viscous prepolymerwas then sampled to determine the extent of the reaction by measuringthe weight percentage of the isocyanate groups (% NCO) of the prepolymerthrough a titration method. The theoretical value of the % NCO after thereaction is completed is 2.80 assuming the glycol MW is at 1800. Tithedetermined % NCO value is higher than the theoretical value, thereaction should be allowed to continue until the theoretical value isreached or the % NCO number becomes constant. Once it was determinedthat the reaction is complete, maintain the prepolymer temperaturebetween 85 and 90° C.

Example 4 Preparation of Aqueous Polymer Dispersion with Prepolymer ofExample 3

The dispersion was prepared by the addition of prepolymer of Example 3using a rotor/stator high speed disperser. The prepolymer as made inExample 3 was transferred directly into the disperser head and dispersedunder high shear forces into deionized water, containing a surfactant, aneutralizer, an anti-oxidant and a foam control agent. Slightly moreprepolymer than required by the dispersion recipe is needed tocompensate for loss in the transfer line and in the reactor.

Table 6 lists the ingredients used in making the dispersion and thecomposition of the dispersion.

TABLE 6 Ingredient CAS Number Unit Quantity Terathane* 1800 251090-06-130.0000 Vestanat* H12MDI 5124-30-1 10.2116 DMPA 4767-03-7 1.02751-Hexanol 111-27-3 0.1692 DI Water 7732-18-5 54.8083 Dowfax 2A1119345-04-9 1.2652 Triethylamine 121-44-8 0.7866 Irganox 245 36443-68-20.6051 Tafigel PUR 61 Mixture 1.0000 BYK 012 Mixture 0.1265 Other 0.0000Total 100.0000

In making a typical batch of this 10 kg dispersion Dowfax 2A1 surfactant(1.2652 kg), an anti-oxidizer Irganox 245 (0.6051 kg), and foam controlagent BYK-012 (0.1265 kg) were mixed and dissolved in the deionizedwater (54.8083 kg). The triethylamine neutralizer (0.7866 kg) was addedto the above water mixture 5 minutes prior to the addition of theprepolymer. The prepolymer (41.4083 kg) maintained at a temperaturebetween 85 and 90° C. was added into the water mixture with high speeddispersing. The addition rate (typically at about 1.5 kg/min or about 30minutes) of the prepolymer should be controlled to allow the formationof uniform dispersion, and the temperature of the dispersion should bekept between 40 and 45° C. Once the addition of prepolymer was complete,mixing was continued for 60 minutes. Then, a thickener Tafigel PUR 61(1.00 kg) was added and allowed to mix for another 60 minutes. Theas-made dispersion was continuously agitated at low speed for 8 hours(or overnight) in the container to eliminate foams and to ensure thereaction had reached completion. The finished dispersion typicallycontains about 42% solids, with viscosity about 4000 centipoises and pHin the range of 7.0 to 8.5.

The dispersion is then filtered through 100 micron bag filters to removebig particles before packed for shipment. It is recommended to use 55gallon metal drums with vented caps, and with a polyethylene linerinside to contain the dispersion for shipment.

Final product specifications were determined as shown in Table 7.

TABLE 7 Parameters Aim ±Limits Method Prepolymer 2.80 0.10 Titration %NCO* Dispersion 44.0 2.0 Microwave Solids, % Dispersion 4000 1000 RVSpindle #3/10 Viscosity, cps** rpm @ 25° C. Dispersion pH 7.7 0.7Dispersion Passing through filter bags no more than 100 micronsFilterability *Sampled 20-30 minutes before the prepolymer is dispersed**Sampled and measured 24 hours after the dispersion is thickened.

Example 5 Comparison of Whiteness Retention

An experiment was conducted to compare the whiteness retention (or“non-yellowing”) of aqueous polyurethane dispersions of the disclosurewith other dispersions. For each dispersion, a sample was prepared bycasting a film on a Mylar sheet with a 10 mil knife and then dried in anitrogen box. The film samples were exposed to different conditions andwhiteness CIE data was collected after each exposure period. Theexposure conditions were thermal (195° C. for five minutes), UV (8hours), fume (24 hours) and NO₂ (24 hours). The thermal exposure testwas conducted in a thermal chamber (Werner-Mathis AG, Typ-Nr., LTF117187) in heated air. The UV exposure test was conducted in AtlasWeather-Ometer® equipped with an Xenon Arc lamp simulating the exposureto daylight, including UV. The NO₂ exposure test was conducted in AtlasWeather-Ometer® in nitrogen oxides atmosphere. For each sample, thecolor of the film before and after exposure was compared; the lower thereduction in CIE, the better the whiteness retention.

Aqueous polyurethane dispersions, i.e., Examples 50-59, were preparedaccording to the compositional makeups shown in Tables 8 and 9.

TABLE 8 Part Number Ex. 50 Ex. 51 Ex. 52 Ex. 53 Ex. 54 (D71206) (D71207)(D80102) (D80110) (D80111) NCO/OH Ratio 1.3726 1.3726 1.5300 1.37261.3700 Meq Acid/kg CG 184.5 183.6 220.0 183.6 185.0 Meq Monol/kg CG 0.0048.20 40.00 48.20 40.00 Mw 49450 48400 46300 Mn 18050 15600 16600Prepolymer: Capped Glycol Recipe, Batch Wt, g 1010.16 1200 1200 12001200 T-1800 Glycol, g 765.00 904.29 861.59 904.29 904.85 PICM, g 220.16260.25 298.10 260.25 260.47 DMPA, g 25.00 29.55 35.41 29.55 29.78Hexanol, g 0.00 5.91 4.90 5.91 4.90 Capping Temp., ° C. 90 90 90 90 90Capping Time, min 120 120 180 180 180 FBV Measured 1175 1070 1040 17871632 Dispersion Recipe Capped glycol 575.00 701.00 681.00 693.00 704.00dispersed, g DI Water, g 1000.00 1000.00 1000.00 1000.00 1000.00Nacconol 90G, g 20.00 20.00 20.00 20.00 20.00 TEA, g 12.67 12.67 12.6712.67 12.67 DeFoo 3000, g 1.00 1.00 1.00 1.00 1.00 Silicone 65, g 5.005.00 5.00 5.00 5.00 Other, g 0.00 0.00 0.00 0.00 0.00 Acrysol RM-8W, g35.00 35.00 35.00 35.00 35.00 Irganox 245, g 10.70 10.70 10.70 10.7010.70 Total Weight, g 1659.37 1785.37 1765.37 1777.37 1788.37

TABLE 9 Part Number Ex. 55 Ex. 56 Ex. 57 Ex. 58 Ex. 59 (D0118) (D80125)(D80129) (D80208) (D80212) NCO/OH Ratio 1.3700 1.5300 1.5300 1.53001.3700 Meq Acid/kg CG 185.0 185.0 185.0 220.0 155.0 Meq Monol/kg CG50.00 40.00 50.00 50.00 30.00 Mw 51000 50200 41700 Mn 16400 19000 15600Prepolymer: Capped Glycol Recipe, Batch Wt, g 1200 1200 1200 1200 1200T-1800 Glycol, g 903.83 879.98 878.97 860.58 920.68 PICM, g 260.27285.34 285.12 297.88 250.69 DMPA, g 29.78 29.78 29.78 35.41 24.95Hexanol, g 6.13 4.90 6.13 6.13 3.68 Capping Temp., 90 90 90 90 90 ° C.Capping Time, min 180 180 180 180 180 FBV Measured 1441 1073 1271 11711478 Dispersion Recipe Capped glycol 700.00 735.00 707.00 699.00 689.00dispersed, g DI Water, g 1000.00 1000.00 1000.00 1000.00 1000.00Nacconol 90G, g 20.00 20.00 20.00 20.00 20.00 TEA, g 12.67 12.67 12.6712.67 12.67 DeFoo 3000, g 1.00 1.00 1.00 1.00 1.00 Silicone 65, g 5.005.00 5.00 5.00 5.00 Other, g 0.00 0.00 0.00 0.00 0.00 Acrysol RM-8W, g35.00 35.00 35.00 35.00 35.00 Irganox 245, g 10.70 10.70 10.70 10.7010.70 Total Weight, g 1784.37 1819.37 1791.37 1783.37 1773.37

Comparative dispersions, F-70 and F-120, were also made according to thecompositional makeups shown in Tables 10 through 13.

TABLE 10 F-70 Prepolymer Composition Ingredient CAS Number Unit QuantityTerathane* 1800 251090-06-1 76.1886 1-Hexanol 111-27-3 0.4070 Mondur* ML26447-40-5 20.9145 DMPA 4767-03-7 2.4898 100.0000

TABLE 11 F-70 Dispersion Composition Ingredient CAS Number Unit QuantityTerathane* 1800 251090-06-1 29.9387 Mondur* ML 26447-40-5 8.2185 DMPA4767-03-7 0.9784 DI Water 7732-18-5 56.8384 Nacconol 90G 25155-30-01.1510 Triethylamine 121-44-8 0.7482 1-Hexanol 111-27-3 0.1606 Additive65 (Dow) mixture 0.2896 DeFoo 3000 mixture 0.0609 Acrysol RM-8W mixture1.0000 Irganox 245 36443-68-2 0.6157 TOTAL 100.0000 Note: The amount ofAcrysol RM-8W may be adjusted to achieve desired dispersion viscosityaim.

TABLE 12 F-120 Prepolymer Composition Ingredient CAS Number UnitQuantity Terathane* 1800 251090-06-1 76.5000 1-Hexanol 111-27-3 0.0000Mondur* ML 26447-40-5 21.0000 DMPA 4767-03-7 2.5000 100.0000

TABLE 13 F-120 Dispersion Composition Ingredient CAS Number UnitQuantity Terathane* 1800 251090-06-1 29.9387 Mondur* ML 26447-40-58.2185 DMPA 4767-03-7 0.9784 DI Water 7732-18-5 56.9990 Nacconol 90G25155-30-0 1.1510 Triethylamine 121-44-8 0.7482 1-Hexanol 111-27-30.0000 Additive 65 (Dow) mixture 0.2896 DeFoo 3000 mixture 0.0609Acrysol RM-8W mixture 1.0000 Irganox 245 36443-68-2 0.6157 TOTAL100.0000 Note: The amount of Acrysol RM-8W may be adjusted to achievedesired dispersion viscosity aim.

The product specifications for these comparative dispersions (F-10 andF-120) are included in Table 14.

TABLE 14 Parameters Aim ±Limits Prepolymer % NCO 1.91 0.25 DispersionSolids, % 40.0 1.0 Dispersion Viscosity, cps 3000 500 Dispersion pH 7.70.7 Dispersion Filterability grits large than 400 microns below 2.5 wt %of the total solids

The difference in CIE whiteness index values before and after exposure(i.e., the results of whiteness retention) are shown in Tables 15(thermal), 16 (UV) and 17 (fume).

TABLE 15 As Is Thermal Thermal Thermal Thermal Thermal Thermal SamplePart CIE avg 1 Min 2 Min 3 Min 4 Min 5 Min Delta Bemis 3410 53.28 58.5357.68 58.01 57.47 57.27 3.99 LYCRA ® T162C 52.87 56.85 55.57 55.89 54.9755.04 2.17 LYCRA ® T162C 53.01 F-120 49.21 46.83 42.03 37.01 30.27 23.81−25.40 F-70 41.26 38.31 31.97 23.25 14.61 6.12 −35.14 Ex. 52 (D80102)55.29 56.13 52.49 47.59 43.11 37.74 −17.56 Ex. 53 (D80110) 52.25 55.8552.45 46.41 40.11 35.68 −16.57 Ex. 54 (D80111) 53.35 Ex. 55 (D80118)52.98 Ex. 56 (D80125) 55.71 56.55 52.71 49.47 43.57 37.03 −18.68 Ex. 57(D80129) 56.38 56.44 52.84 47.95 43.51 36.46 −19.92 Ex. 58 (D80208)56.88 55.35 51.35 46.77 41.94 37.36 −19.52 Ex. 59 (D80212) 51.56 Mylarcontrol 54.81 56.99 58.47 58.04 57.51 57.26 2.45

TABLE 16 UV UV UV UV Sample Part 2 Hr 4 Hr 8 Hr Delta Bemis 3410 58.1857.44 57.81 4.53 LYCRA ® T162C 57.86 57.86 57.58 4.71 LYCRA ® T162C57.86 57.86 58.42 5.41 F-120 33.08 25.66 18.87 −30.34 F-70 34.14 34.1429.29 −11.97 Ex. 52 (D80102) 54.45 54.92 55.85 0.55 Ex. 53 (D80110)57.25 57.31 58.49 6.25 Ex. 54 (D80111) Ex. 55 (D80118) Ex. 56 (D80125)55.11 55.15 56.22 0.51 Ex. 57 (D80129) Ex. 58 (D80208) 54.19 54.19 55.62−1.26 Ex. 59 (D80212) 55.21 55.21 55.24 3.68 Mylar control 58.64 59.2759.93 5.12

TABLE 17 NO2 NO2 NO2 NO2 Fume Fume Fume Fume Sample Part 8 Hr 16 Hr 24Hr Delta 8 Hr 16 Hr 24 Hr Delta Bemis 3410 58.74 58.40 53.67 0.39LYCRA ® T162C LYCRA ® T162C 58.54 59.01 51.00 −2.01 F-120 F-70 32.6821.38 5.85 −35.41 Ex. 52 (D80102) Ex. 53 (D80110) Ex. 54 (D80111) 57.7157.71 51.21 −2.14 51.76 54.47 52.92 −0.43 Ex. 55 (D80118) 57.94 56.8855.08 2.11 53.23 52.16 49.12 −3.86 Ex. 56 (D80125) 56.15 55.77 55.38−0.33 Ex. 57 (D80129) 56.46 55.81 56.2 −0.18 53.62 51.99 48.85 −7.53 Ex.58 (D80208) 53.67 52.47 49.99 −6.89 Ex. 59 (D80212) 57.69 58.11 56.935.37 Mylar control 57.30 59.43 59.06 4.25 59.58 59.10 58.70 3.89

The results of the whiteness retention test are graphically depicted inFIGS. 21 through 23. “Inventive (average)” is an average of Examples50-59. For comparison, TPU Film, which is a commercially extruded film(Bemis 3410), and a conventional commercially available Spandex PolymerFilm (LYCRA® T162C) is included, as well as the results of samplesprepared using comparative formulas F-70 and F-120, which were filmscast from polyurethane dispersions with aromatic diisocyanates.

The films made from dispersions of the present disclosure (Inventive(average)) showed better whiteness retention than films of F-70 andF-120, especially after UV and NO₂ exposures. This is expected to be dueto inclusion of an aliphatic diisocyanate (i.e., PICM) in thecompositions of the present disclosure, as opposed to an aromaticisocyanate (i.e., Mondur® ML) in F-70 and F-120.

Film properties are included in Tables 18 and 19.

TABLE 18 Meq Meq Sample NCO/OH Acid/kg Monol/kg TP1 TP2 TP301 TP3 DECPart Ratio* CG CG (g/den) (g/den) (g/den) (g/den) (%) Ex. 54 (D80111)1.3700 185.0 40.00 0.0062 0.0064 0.0066 0.0033 33.46 Ex. 52 (D80102)1.5300 220.0 40.00 0.0133 0.0163 0.0195 0.0097 20.28 Ex. 55 (080118)1.3700 185.0 50.00 0.0062 0.0062 0.0062 0.0028 38.82 Ex. 57 (D80129)1.5300 185.0 50.00 0.0107 0.0123 0.0139 0.0078 24.79 Ex. 56 (D80125)1.5300 185.0 40.00 0.0108 0.0137 0.0166 0.0095 24.52 Ex. 58 (D80208)1.5300 220.0 50.00 0.0109 0.0131 0.0154 0.0086 25.30 Ex. 59 (D80212)1.3700 155.0 30.00 0.0049 0.0055 0.0059 0.0021 39.68 F-120 1.373 184.50.00 0.0193 0.0256 0.0358 0.0223 11.11 F-70 1.370 185.0 40.00 0.01370.0173 0.0220 0.0112 13.01 *Excluding OH from monol terminator.

TABLE 19 TM2 TM1 ELO TEN SET Sample Part (g/den) (g/den) (%) (g/den) (%)Ex. 54 (D80111) 0.0008 0.0000 1000.00 0.0098 98.35 Ex. 52 (D80102)0.0034 0.0001 620.02 0.0330 88.10 Ex. 55 (D80118) 0.0004 0.0000 187.760.0062 80.71 Ex. 57 (D80129) 0.0028 0.0000 854.44 0.0499 154.25 Ex. 56(D80125) 0.0033 0.0004 699.11 0.0469 256.71 Ex. 58 (D80208) 0.00290.0000 733.00 0.0384 113.54 Ex. 59 (D80212) 0.0003 0.0000 999.44 0.0064129.57 F-120 0.0104 0.0062 618.78 0.1332 26.64 F-70 0.0045 0.0016 586.560.0281 46.81

The abbreviations used in Tables 18 and 19 have the following meanings:

Meq is the milliequivalent of the specific functional groups, such ascarboxylic acid or hydroxyl terminating groups. For dispersions of thepresent disclosure, they are expressed as milliequivalent per kg of theprepolymer or capped glycol (CG).

TP1, TP2, TP301, TP3 represent the load power. This is the force when afilm sample is stretched to a certain percentage in a specific stretch(0-300%) cycle. TN means that the film is stretched to 100%. TP2 meansthe stretch force (also called load power) that the film is stretched to200% in the first 0 to 300% stretch cycles. TP301 means that the film isstretched to 300% in the first stretch cycle. TP3 means that the film isstretched to 300% in the fifth stretch cycle.

DEC is a stress decay measurement. When the film sample is stretched forthe 5^(th) time to 300% elongation, this determines the force (5TP300).When the sample is held at this elongation for 30 seconds, the forcewill drop due to stress relaxation. The force data collected afterholding for 30 seconds, right before releasing the tension for recovery,is 5TM300.

DEC=(5TP300−5TM300)×100/5TP300

TM2 is the recovery force (also called unload power) of the film samplemeasured at 200% elongation in the 5^(th) 0 to 300% stretch cycle.

TM1 is the recovery force or unload power of the film sample after DECmeasurement, measured at 100% elongation in the 5^(th) stretch cycle.

ELO is the break elongation when the film sample is stretched in thesixth cycle.

TEN is the tensile strength or tenacity when the film sample isstretched in the sixth cycle.

SET is the unrecovered set after 5 stretch cycles when the recoveryforce of the film sample reaches to zero.

Because the film samples had different thicknesses, the force data wasnormalized in terms of grams per denier.

Example 6 Comparison of Tensile Strength

An experiment was conducted to improve the tensile strength of filmsmade from aqueous polyurethane dispersions of the disclosure and comparethem with comparative examples, F-70 and F-120.

As shown in Table 20 (which reconfigures data presented in Tables 18 and19 above), under the same compositional control parameters, films madefrom F-70 and F-120 had better balanced tensile properties (higher loadand unload power, higher tenacity) than films of the present disclosure.

TABLE 20 Meq Meq Sample NCO/OH Acid/kg Monol/kg TP2 DEC TM2 TEN SET PartRatio CG CG (g/den) (%) (g/den) (g/den) (%) Ex. 54 1.3700 185.0 40.000.0064 33.46 0.0008 0.0098 98.35 Ex. 55 1.3700 185.0 50.00 0.0062 38.820.0004 0.0062 80.71 Ex. 59 1.3700 155.0 30.00 0.0055 39.68 0.0003 0.0064129.57 F-120 1.373 184.5 0.00 0.0256 11.11 0.0104 0.1332 26.64 F-701.370 185.0 40.00 0.0173 13.01 0.0045 0.0281 46.81

New samples as shown in Table 21 were prepared modifying the NCO/OHratio and amount of monol terminator (Meq Monolikg CG). After testingthe tensile strength of these new samples (Examples 60-65), it was foundthat the tensile performance improved with an increase in NCO/OH ratioover 1.370 and/or reduced terminator (Meq Monol/kg CG).

TABLE 21 Ex. 60 Ex. 61 Ex. 62 Ex. 63 Ex. 64 Ex. 65 Part Number (D160317)(D160318) (D160322) (D160318-2) (D160329) (D160331) NCO/OH Ratio 1.60001.5000 1.8000 1.5000 1.9000 2.0000 % NCO Aim 2.9717 2.5060 3.8707 2.50604.3049 4.7292 Meq Acid/kg CG 185.0 185.0 185.0 185.0 185.0 185.0 MeqMonol/kg CG 0.00 0.00 0.00 0.00 0.00 0.00 pH pH--6.56 pH--6.60 pH--6.95pH--7.50 pH--6.72 pH--6.76 Prepolymer:Capped Glycol 1200 1200 1200 12001200 1200 Recipe, Batch Wt, g T-1800 Glycol, g 873.37 888.59 843.97888.59 829.78 815.90 PICM, g 296.86 281.63 326.25 281.63 340.45 354.32DMPA, g 29.78 29.78 29.78 29.78 29.78 29.78 Hexanol, g 0.00 0.00 0.000.00 0.00 0.00 Catalyst, mg 0.00 0.00 0.00 0.00 0.00 0.00 Capping Temp.,° C. 90 90 90 90 90 90 Capping Time, min 240 240 240 240 240 240 FBVMeasured 1749 1208 1047 3164 779 568 Dispersion Recipe Capped glycol746.60 802.60 759.30 714.90 779.00 779.10 dispersed, g DI Water, g1000.00 1000.00 1000.00 1000.00 1000.00 1000.00 Dowfax 2A1, g 23.0023.00 23.00 23.00 23.00 23.00 TEA, g 14.12 14.12 14.12 14.12 14.12 14.12BYK 012, g 2.30 2.30 2.30 2.30 2.30 2.30 Silicone 65, g 0.00 0.00 0.000.00 0.00 0.00 Other, g 0.00 0.00 0.00 0.00 0.00 0.00 Thickener, g 18.5018.50 18.50 18.50 18.50 18.50 Irganox 245, g 11.00 11.00 11.00 11.0011.00 11.00 Total Weight, g 1818.92 1871.52 1828.22 1783.82 1847.921848.02 Calculated Total 43.88 45.46 44.16 42.77 44.76 44.76 Solids, wt%

TABLE 22 NCO/OH Meq Meq 1TP100 1TP200 1TP300 5TP100 5TP200 5TP300 PartRatio Acid/kg CG Monol/kg CG (g/den) (g/den) (g/den) (g/den) (g/den)(g/den) Ex. 63 1.500 185.0 0.00 0.0223 0.0300 0.0420 0.0144 0.02140.0307 Ex. 60 1.600 185.0 0.00 0.0266 0.0380 0.0592 0.0164 0.0251 0.0397Ex. 62 1.800 185.0 0.00 0.0354 0.0530 0.0911 0.0189 0.0306 0.0585 Ex. 641.900 185.0 0.00 0.0394 0.0605 0.1311 ** ** ** Ex. 65 2.000 185.0 0.00*** *** *** *** *** *** F-120 1.373 184.5 0.00 0.0193 0.0256 0.03580.0223 F-70 1.370 185.0 40.00 0.0137 0.0173 0.0220 0.0112 ** Filmstripes were broken before completing the 5 stretch cycles of 0-300%.*** Film was too rigid to be peeled off back paper with good enoughquality for the instron test.

TABLE 23 NCO/OH DEC TM2 TM1 ELO TEN SET Part Ratio (%) (g/den) (g/den)(%) (g/den) (%) Ex. 63 1.500 16.34 0.0144 0.0094 522.80 0.1810 21.84 Ex.60 1.600 20.00 0.0156 0.0104 494.83 0.2191 21.57 Ex. 62 1.800 24.830.0171 0.0107 406.67 0.1543 24.60 Ex. 64 1.900 ** ** ** ** ** ** Ex. 652.000 *** *** *** *** *** *** F-120 1.373 11.11 0.0104 0.0062 618.780.1332 26.64 F-70 1.370 13.01 0.0045 0.0016 586.56 0.0281 46.81 ** Filmstripes were broken before completing the 5 stretch cycles of 0-300%.*** Film was too rigid to be peeled off back paper with good enoughquality for the instron test.

Meq Acid or Monol/kg CG, Denier, TP, DEC, TM, ELO, TEN, and SET inTables 22 and 23 have the same meanings as above in Tables 18 and 19. Inaddition, for example, 1TP100 means that the film is stretched to 100%or 2 times of its original length in the first (0-300%) stretch cycle;5TP200 means that the film sample is stretched to 200% or 3 times of itsoriginal length in the fifth (0-300%) stretch cycle. After stretchingfor 5 cycles, the film sample is stretched again all the way until it isbroken.

As shown in the data presented in Tables 22 and 23, it was found thatthe best tensile properties for films of the present disclosure weremade from dispersions having NCO/OH ratios in between 1.50 to 1.90, withthe polymer number average molecular weight larger than 10,000. When theNCO/OH ratios were below 1.50, the films had inadequate power(stretch/recovery), and when the NCO/OH ratios were above 1.90 the filmswere brittle with low elongation.

Example 7 Improved Chlorine Resistance

An experiment was conducted to evaluate chlorine resistance of fabricsto which an aqueous dispersion of the present disclosure has beenapplied. The fabrics were tested for durability of stretch and recoveryproperties to chlorine exposure according to the following procedure.Chlorinated water conditions (also referred to as a chlorinatedenvironment, to simulate a conventional chlorinated pool) were createdby maintaining a water bath at 25° C., pH at 7.5, and an activatedchlorine level at 3.5 ppm. The fabric samples are then fully submergedin the water bath, while they were continuously stretched from 0 to 40%at a rate of 24 times per minute for a period of 240 hours. Three timeseach hour, the amount of load in grams required to elongate the fabricto 40% was measured and recorded. At the end of a 240 hour exposure, thepercentage change between the starting load at 0 hours and the load atother measured time periods (e.g., after 180 hours of submersion) wascalculated. Additionally, after the fabrics were removed from thechlorine bath and allowed to air dry until dry to the touch, the fabricswere visually inspected for breakage or integrity of the applied anddried aqueous dispersion.

A circular knit fabric (Fabric A) was produced on a 28GG machine bycombining 69% of a 40 denier-34 filament Nylon 6,6 yarn and 31% of a 55denier spandex (LYCRA® fiber type 275Z). The fabric was made usingconventional textile processing. A sample of this fabric was treatedwith an aqueous polyurethane dispersion of Example 2 above byconventional screen printing, followed by a curing step in which thefabric was heated to 160° C. for 60 seconds.

Performance and chlorine resistance of the fabric with and withoutapplication of the inventive aqueous polyurethane dispersion are shownin Table 25 below. Specifically, Table 25 shows the load (or fabricmodulus) to 40% elongation at certain time intervals after submersion inthe chlorinated environment. As shown Table 25, after application andcuring of the dispersion, the fabric modulus to 40% elongation increasedby 43% (from 505 g to 723 g). After testing the modulus of the samplesafter chorine exposure at different tested time periods, the stretchforce in fabric with the dispersion (“Fabric A PLUS”) compared to thestretch force in Fabric A was always 30% or more greater. At 180 hours,the increase in fabric modulus between the samples was measured as 41%,which is almost the same as the initial measured difference at 0 hoursof 43%.

At 180 hours, the fabric modulus to 40% elongation increased by 41%after exposure to the chlorinated conditions (from 320 g to 453 g). Thisconfirms an unexpected superior commercial purpose and use of theinventive aqueous polyurethane dispersion to increase modulus in adurable manner in a chlorinated environment.

After 180 hours in the chlorinated bath, Fabric A PLUS and the untreatedsample of Fabric A show the same 63% decrease on an absolute basis inload to elongate. This confirms that the performance of the fabric isunchanged, on a percentage basis, between the two samples. Takentogether, these results are particularly surprising considering that thedispersion did not contain additional technologies, such as thosedescribed in U.S. Pat. No. 5,626,960, which are known in the art toimprove the resistance of polyurethane based materials to propertydegradation from exposure to activated chlorine. It is understood thatshould one desire to improve the performance even further, one may alsoinclude an additive, such as those described in U.S. Pat. No. 5,626,960.

TABLE 25 Load to Elongate 40% of Fabric Samples in ChlorinatedEnvironment Load to % decrease of Elongate load after 180 Fabric 40%(g)- hrs in chlorine Sample 0 hr 20 hr 60 hr 100 hr 140 hr 180 hrenvironment Fabric A 505 493 484 457 396 320 63% (Control) Fabric A 723653 629 602 542 453 63% PLUS (Fabric A with Dispersion Applied) %Increase in 43% 32% 30% 32% 37% 41% Force due to the applied Dispersion

Example 8 Aqueous Polyurethane Dispersion Containing DMAMP

An aqueous polyurethane dispersion was prepared using DMAMP and EDA asneutralizers instead of TEA, according to the compositional makeup shownin Table 26.

TABLE 26 Example 80 NCO/OH Ratio 1.6000 % NCO Aim 2.9717 Meq Acid/kg CG185.0 Meq Monol/kg CG 0.00 Capped Glycol Recipe, Batch Wt, g 1200 T-1800Glycol, g 873.37 PICM, g 296.86 DMPA, g 29.78 Hexanol, g 0.00 Catalyst,mg 120 (K-KAT 640) Capping Temp., ° C. 90 Capping Time, min 150 FBVMeasured Dispersion Recipe Capped glycol dispersed, g 750.00 DI Water, g1100.00 Dowfax 2A1, g 23.00 DMAMP, g 20.33 BYK 012, g 2.30 Silicone 65,g 0.00 EDA, g 7.97 Thickener, g 18.00 Irganox 245, g 11.00 Total Weight,g 1932.60 Calculated Total Solids, wt % 41.62

The film properties of Example 80 were tested. The results are shownbelow in Tables 27 and 28 also with the film properties for Examples 60,62, 63 and 64 (also shown above in Tables 23 and 24).

TABLE 27 Meq NCO/OH Acid/kg 1TP100 1TP200 1TP300 5TP100 Part Ratio CG(g/den) (g/den) (g/den) (g/den) Ex. 80 1.600 185.0 0.0314 0.0446 0.07170.0145 (DMAMP) Ex. 63 1.500 185.0 0.0223 0.0300 0.0420 0.0144 Ex. 601.600 185.0 0.0266 0.0380 0.0592 0.0164 Ex. 62 1.800 185.0 0.0354 0.05300.0911 0.0189 Ex. 64 1.900 185.0 0.0394 0.0605 0.1311 * *Film stripeswere broken before completing the 5 stretch cycles of 0-300%.

TABLE 28 5TP200 5TP300 DEC TM2 TM1 ELO TEN SET Part (g/den) (g/den) (%)(g/den) (g/den) (%) (g/den) (%) Ex. 80 0.0233 0.0390 24.44 0.0122 0.0069542.20 0.2247 34.48 (DMAMP) Ex. 63 0.0214 0.0307 16.34 0.0144 0.0094522.80 0.1810 21.84 Ex. 60 0.0251 0.0397 20.00 0.0156 0.0104 494.830.2191 21.57 Ex. 62 0.0306 0.0585 24.83 0.0171 0.0107 406.67 0.154324.60 Ex. 64 * * * * * * * * * Film stripes were broken beforecompleting the 5 stretch cycles of 0-300%.

As evident from a review of Tables 27 and 28, films made using DMAMPhave comparable improved tensile properties (higher load and unloadpower, higher tenacity) to films made using TEA.

As those skilled in the art will appreciate, numerous changes andmodifications may be made to the embodiments described herein, withoutdeparting from the spirit of the disclosure. It is intended that allsuch variations fall within the scope of the invention.

1-34. (canceled)
 35. A bust supporting garment comprising: a materialdefining a breast cup including a lower periphery and a side peripherythat extends from said lower periphery to a top portion of the breastcup where a strap is optionally attached, and a winged portion; and afilm adhered to at least a portion of the material, said film comprisinga dried aqueous polyurethane dispersion including a prepolymer, saidprepolymer comprising: a glycol, an aliphatic diisocyanate and a diol,wherein a ratio of isocyanate groups in the aliphatic diisocyanate tohydroxy groups in the glycol and the diol (NCO/OH) is about 1.30 toabout 2.20.
 36. The bust supporting garment of claim 35, wherein thebreast cup comprises a pair of breast cups, each of said breast cupsincludes the lower periphery and the side periphery that extends fromsaid lower periphery to the top portion of each of said breast cups. 37.The bust supporting garment of claim 36, wherein the film is adhered toat least a portion of the material at the lower and/or side peripheriesof the breast cups.
 38. The bust supporting garment of claim 35, whereinthe film is adhered to at least the wing portions.
 39. The bustsupporting garment of claim 35, wherein the film is adhered to thestraps of the garment.
 40. The bust supporting garment of claim 35,wherein the film is a continuous film in the form of a triangular shape,a trapezoid shape, or a narrow strip.
 41. The bust supporting garment ofclaim 35, wherein the garment is a brassiere, bralette or sports bra.42. The bust supporting garment of claim 35, wherein the breast cup isformed without underwire, seams, padding, lining, foam, panels, or thelike.